Colored nylon, its manufacturing method and use

Abstract

This invention relates to a manufacturing technology for colored nylon, and more particularly to colored nylon, its manufacturing method, and its use. The colored nylon of this invention contains nylon structural units and color-developing structural units, the color-developing structural units contain dye color-developing groups, the chromaticity of the supernatant liquid obtained by mixing the colored nylon and an organic solvent in a weight ratio of 1:3 and steaming is 10 or less, and the difference in color intensity of the colored nylon is 0.2 or less. The manufacturing method of the colored nylon of this invention includes the step of bringing a condensate containing dye color-developing groups into contact with a nylon monomer to carry out a condensation reaction so that at least a portion of the dye color-developing groups are located between and / or at the ends of structural units formed by nylon units. The colored nylon according to this invention has excellent water resistance and organic solvent resistance, high dye uniformity, excellent dye stability, and furthermore, its manufacturing process consumes little energy, produces little pollution, and offers great economic and social benefits.

Description

Detailed description of the invention

[0001] [Cross-reference of related applications] This invention claims the benefits of Chinese Patent Application No. 202310118815.9, filed on 31 January 2023, and Chinese Patent Application No. 202410096657.6, filed on 23 January 2024, the contents of which are incorporated herein by reference.

[0002] [Technical field] This invention relates to a nylon synthesis technique, and more specifically to colored nylon, a method for producing the colored nylon, and its use.

[0003] [Background technology] Nylon is a polyamide product characterized by high tensile strength, high modulus of elasticity, and excellent abrasion resistance and self-lubrication. It is widely used in industries such as automobile manufacturing, electronics and electrical equipment, machinery and equipment, and packaging, and is a highly durable chemical fiber second only to polyester.

[0004] Nylon includes aliphatic nylon, aliphatic-aromatic nylon, and aromatic nylon. Among these, aliphatic nylon has advantages such as excellent toughness, self-lubrication, abrasion resistance, chemical resistance, gas permeability, and oil resistance, and is widely used in fields such as the textile industry, industrial fibers, and daily engineering materials. Aromatic nylon has excellent mechanical properties, insulation, chemical stability, and very high thermal properties due to the aromatic groups in its molecular chains, and is currently mainly used in industries such as aerospace, nuclear industry, and electronics and electrical industry.

[0005] Nylon substrates need to be dyed in various colors depending on the requirements of the application scene in order to meet the needs of various products. Conventional nylon dyeing methods mainly consist of immersion dyeing and stock dyeing. Among these, immersion dyeing generally employs a process in which the nylon substrate is mixed with an acidic dye and dyed at high temperature. Stock dyeing involves adding an appropriate colorant to a spinning solution, thoroughly mixing, dissolving, and filtering it. The colorant or colored stock can also be injected before it enters the spinneret. However, the dyeing effect of immersion dyeing and stock dyeing is mainly achieved by physical forces such as hydrogen bonds, Coulomb forces, and van der Waals forces between the dye and the nylon substrate, making it difficult to control the uniformity of the dyeing, resulting in poor stability, and discoloration and fading are particularly likely to occur in organic solvents.

[0006] Conventional techniques include methods for introducing dye groups into nylon in the form of chemical bonds. For example, CN112457486A polymerizes polyamide monomers in the presence of a light absorber to produce a polyamide having a light absorber in the polyamide main chain, and the light absorber is selected from polyamine light absorbers, polyacid light absorbers, amino acid light absorbers, and any combination thereof. However, processes that copolymerize by directly adding dyes to a nylon system have obvious problems, such as incomplete dyeing reactions, poor water resistance after dyeing, and uneven dyeing.

[0007] [Overview of the prefecture] [Problems the invention aims to solve] The object of the present invention is to provide colored nylon, a method for producing the same, and a method for using the same, in order to solve the problems of the prior art, such as poor physical dyeing stability, low efficiency of chemical dyeing reactions, uneven dyeing, and severe contamination.

[0008] [Means for solving the problem] According to a first aspect of the present invention, the present invention provides a colored nylon comprising a nylon structural unit and a color-developing structural unit, wherein the color-developing structural unit comprises a dye color-developing group, the chromaticity of the supernatant liquid obtained by mixing the colored nylon and an organic solvent in a weight ratio of 1:3 and steaming is 10 or less, and the difference in color intensity of the colored nylon is 0.2 or less.

[0009] According to a second aspect of the present invention, the present invention provides a method for producing colored nylon, comprising the step of bringing a condensate containing dye color groups into contact with a nylon monomer to carry out a condensation reaction so that at least a portion of the dye color groups are located between and / or at the ends of structural units formed by nylon units.

[0010] According to a third aspect of the present invention, the present invention provides colored nylon manufactured by the above method.

[0011] According to a fourth aspect of the present invention, the present invention provides the use of the above-mentioned colored nylon in at least one of spinning, industrial fibers, and engineering materials.

[0012] [Effects of the invention] According to the above technical solution, the colored nylon according to the present invention does not fade even after steaming in an organic solvent and has excellent dyeing stability and color fastness. The colored nylon has excellent dyeing uniformity, the difference in color intensity is 0.2 or less, and it has excellent water resistance.

[0013] The method for producing colored nylon according to the present invention solves the problem of low dye reaction rate and utilization rate that exists in conventional processes where amine dyes polycondensate amines and diamines and diacids or dicarboxylic acid halides, because the amine dye has a much lower reactivity ratio than the diamine used to produce the nylon, by contacting nylon or nylon monomers or dicarboxylic acid chromogenic groups of dye in the form of a condensate. At the same time, it is possible to uniformly disperse the dye and strengthen its bonds. Furthermore, since the dye-containing polycondensate is easily separated from the dye, it is easy to fully utilize the dye, thereby avoiding the generation of dye-containing wastewater in subsequent processes. Colored nylon produced by the method of the present invention has high dye uniformity, excellent stability, and high color fastness, and does not fade even after steaming with organic solvents. Furthermore, in this manufacturing process, the product obtained by the condensation reaction can be cooled directly and used for nylon processing, effectively reducing subsequent processing steps, avoiding the generation of dye-containing wastewater, thereby reducing energy consumption, water consumption, and chemical consumption and COD emissions. This results in high environmental protection, a shortened process flow, and effectively enhances the economic and social benefits of colored nylon production.

[0014] Other features and advantages of the present invention will be described in detail in the following sections on embodiments for carrying out the invention.

[0015] [Brief description of the drawing] [Figure 1] Infrared spectra of the dye monomer, dibasic acid, and dye condensate 1-1 in Production Example 1.

[0016] [Figure 2] Infrared spectra of dye condensate 1-1, caprolactam, and colored nylon in Example 1.

[0017] [Figure 3] This is a comparison of the black nylon-6 polymer slices produced in Example 31 before and after steaming with ethyl acetate, where a is before steaming and b is after steaming.

[0018] [Figure 4] This is a comparison of black nylon-6 produced in Comparative Example 12 before and after steaming with ethyl acetate, where a is before steaming and b is after steaming.

[0019] [Figure 5] Condensate 2-1 produced in manufacturing example 15 1 This is an H NMR spectrum.

[0020] [Figure 6] This is the infrared spectrum of condensate 2-1 produced in manufacturing example 15.

[0021] [Figure 7] Condensates 2-3 produced in manufacturing example 17 1 This is an H NMR spectrum.

[0022] [Figure 8] This is the infrared spectrum of condensate 2-3 produced in manufacturing example 17.

[0023] [Figure 9] Condensates 2-7 produced in manufacturing example 21 1 This is an H NMR spectrum.

[0024] [Figure 10] This is the infrared spectrum of condensate 2-7 produced in manufacturing example 21.

[0025] [Figure 11] This is the infrared spectrum of the yellow nylon-6 polymer produced in Example 25.

[0026] [Figure 12] This is the infrared spectrum of the black nylon-6 polymer produced in Example 31.

[0027] [Figure 13] This is the infrared spectrum of the brown nylon-6 polymer produced in Example 44.

[0028] [Figure 14] Condensate, dye monomer, and dibasic acid produced in Production Example 2 1 This is an H NMR spectrum.

[0029] [Figure 15] Liquid chromatograms of the condensate, dye monomer, and dibasic acid produced in Production Example 2.

[0030] [Modes for carrying out the invention] The endpoints and any values ​​of the ranges disclosed herein should be understood to include values ​​close to those exact ranges or values, rather than being limited to those exact ranges or values. With respect to numerical ranges, one or more new numerical ranges can be obtained by combining the endpoint values ​​of each range, the endpoint values ​​of each range with individual dot values, and the individual dot values, and these numerical ranges are deemed to be specifically disclosed herein.

[0031] A first aspect of the present invention provides a colored nylon, the colored nylon containing nylon structural units and color-developing structural units, the color-developing structural units containing dye color-developing groups, the chromaticity of the supernatant liquid before and after steaming the colored nylon and an organic solvent in a weight ratio of 1:3 is 10 or less, and the difference in color intensity of the colored nylon is 0.2 or less.

[0032] The colored nylon according to the present invention exhibits stable colorfastness even after steaming in an organic solvent (e.g., ethyl acetate, ethanol, methanol, acetone, etc.), and does not fade. When the chromaticity of the supernatant liquid after steaming in an organic solvent was detected by the dilution factor method, it was found that the chromaticity of the supernatant liquid after steaming was 10 or less, confirming that the colored nylon according to the present invention is resistant to steaming in organic solvents and has clearly excellent dyeing stability and colorfastness. Furthermore, since the difference in color intensity of the colored nylon is 0.2 or less, the colored nylon has excellent dyeing uniformity and excellent water resistance.

[0033] The inventors, in order to solve the problems of the prior art, conducted extensive and in-depth research and found that by contacting the dye coloring group with nylon or nylon monomer in the form of a condensate, involving it in the polymerization system of nylon, and achieving a high reactivity ratio between the dye coloring group and nylon monomer via an oligomer, the dye coloring group is efficiently and uniformly introduced into the nylon segment. As a result, the excellent mechanical properties of the nylon product are maintained, and the resulting colored nylon has high dye uniformity, excellent stability, high color fastness, and does not fade even after steaming with an organic solvent, thus possessing excellent water resistance and dye uniformity.

[0034] In the present invention, the process for testing the mixture of colored nylon and organic solvent and steaming is as follows: After mixing colored nylon and ethyl acetate in a weight ratio of 1:3, the mixture is refluxed and steamed at 77°C for 24 hours, filtered to remove solid colored nylon, and then the chromaticity of the supernatant liquid of ethyl acetate after steaming is measured in reference to HJ1 182-2021 "Water Quality - Measurement of Chromaticity: Dilution Factor Method," and the chromaticity is expressed as a dilution factor value.

[0035] To compare and analyze the difference in dye uniformity between the colored nylon according to the present invention and the colored nylon of the prior art, the effect of dye uniformity of the colored nylon is characterized by using the standard deviation △K / S (i.e., the difference in color intensity Sr) of the ratio K / S of the colorant absorption coefficient K to the colorant scattering coefficient S at multiple test points of the colored nylon. The specific test process is as follows: The K / S values ​​at various positions on a nylon slice are measured using a Datacolor 850 colorimeter (eight measurement points are selected along two diagonals and two long sides for each slice), and the obtained K / S values ​​are used as sample data. The difference in color intensity, expressed as Sr, is obtained by calculating its standard deviation.

[0036] In the present invention, the process for detecting the halogen ion content in a boiled solution obtained by mixing colored nylon and deionized water in a weight ratio of 1:1 and steaming is as follows: Colored nylon and deionized water are mixed in a weight ratio of 1:1, and a boiled solution is obtained by steaming at 90-110°C for 3-6 hours. This boiled solution is sampled and the concentration of free halogen ions is measured by ion chromatography. Note that the manufacturing process of colored nylon according to the present invention does not use acid chlorides and halide substrates, so no residual halogen ions are present in the colored nylon, and even after mixing with deionized water and steaming at any temperature for any time, no halogen ions are present in the boiled solution. More preferably, the halogen ion content in the boiled solution obtained by mixing the halogen of the colored nylon with deionized water in a weight ratio of 1:1 and steaming is 5 ppm or less.

[0037] In this invention, the water color fastness of the colored nylon is measured in accordance with the international standard ISO 105-E01, and the water color fastness of the colored nylon is grade 4 to 5. It has been found that the colored nylon according to the present invention has excellent water resistance.

[0038] In this invention, the sweat colorfastness of colored nylon is measured in accordance with the international standard ISO 105-E04, and the soap wash colorfastness of colored nylon is measured in accordance with the international standard ISO 105-C10. The sweat colorfastness of the colored nylon is grade 4 to 5, and the soap wash colorfastness is grade 4 to 5. It has been found that the colored nylon according to the present invention not only has improved dye uniformity and water resistance, but also excellent sweat resistance and soap resistance.

[0039] In this invention, since colored nylon contains dye-developing groups, it is found that the nylon has a desired color, and the contained dye-developing groups can be determined by nuclear magnetic resonance and infrared spectroscopy. For example, the dye-developing group is an anthraquinone group, and in the nylon product thereof, the infrared spectrum is 3085 cm⁻¹. -1 A =CH stretching vibration peak (corresponding to =CH in the anthraquinone structure) is observed nearby, and at 1553 cm -1A stretching vibration peak of the benzene core skeleton (corresponding to the benzene core skeleton of the anthraquinone structure) can be seen nearby. When the dye coloring group is an acid black group, the infrared spectrum of nylon products shows 1588 cm⁻¹. -1 A characteristic peak of carbon-nitrogen double bonds can be seen in the vicinity, at 1487–1460 cm⁻¹. -1 A characteristic peak of cyclohexadienyl can be seen nearby. Preferably, the dye chromogenic group is at least one selected from anthraquinone chromogenic group, solvent black group, acid black group, acid blue group, and acid yellow group.

[0040] In the present invention, the content of nylon structural units and color-developing structural units in colored nylon can be measured by nuclear magnetic resonance spectroscopy and infrared spectroscopy. More preferably, the content of color-developing structural units is 0.2 to 1.5% by weight, based on the weight of the colored nylon.

[0041] A second aspect of the present invention provides a method for producing colored nylon, the method comprising the step of bringing a condensate containing dye-developing groups into contact with a nylon monomer to carry out a condensation reaction such that at least a portion of the dye-developing groups are located between and / or at the ends of structural units formed by nylon units.

[0042] The method for producing colored nylon according to the present invention involves contacting the dye coloring group with the nylon monomer in the form of a condensate, involving it in the polymerization system of the nylon, and achieving a high reactivity ratio between the dye coloring group and the nylon monomer via the condensate. This efficiently introduces the dye coloring group into the nylon segment, improving the reaction rate and utilization rate of the dye, while uniformly distributing the dye in the nylon segment and strengthening the bond. As a result, the colored nylon has high dye uniformity (difference in color intensity is 0.2 or less), excellent dye stability, high color fastness, no fading even after steaming with organic solvents, and excellent water resistance.

[0043] The manufacturing method according to the present invention allows for efficient polymerization of dye colorants and nylon monomers, and the product obtained by the condensation reaction contains very few impurities, such as unreacted condensates containing dye colorants. The product of the condensation reaction can be directly subjected to subsequent processing such as slicing after cooling. Therefore, this manufacturing process effectively reduces subsequent processing steps, avoids the generation of dye-containing wastewater, and thereby reduces energy consumption, water consumption, chemical consumption, and COD emissions, resulting in high environmental protection, a shortened process flow, and high economic and social benefits.

[0044] According to the present invention, a condensate containing dye-developing groups can be linked to a nylon segment via any form of chemical bonding to form a nylon polymer into which dye-developing groups have been introduced. Preferably, the nylon monomers in the polymer are linked to the condensate containing dye-developing groups via amide bonds. In this preferred case, the block stability of the dye-developing groups in the nylon segment is further improved, thereby improving the dyeing stability of the colored nylon. In the present invention, the dye coloring group may be at least one selected from anthraquinone coloring group, solvent black group, acid black group, acid blue group, and acid yellow group.

[0045] As an embodiment of the present invention, the structural formula of the condensate containing the dye color group is shown by formula (I).

[0046] [ka]

[0047] Here, R1 is an aliphatic alkylene or an aromatic alkylene, and Q' is the dye chromophore group. In the present invention, R1 may be any aliphatic alkylene, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, octylene, undecylene, dodecylene, or any aromatic alkylene, such as terephthalylidene, phthalylidene, isophthalylidene, 1,3-naphthalenedimethylene, 1,4-naphthalenedimethylene, 1,5-naphthalenedimethylene, 1,7-naphthalenedimethylene, 2,6-naphthalenedimethylene, and 2,7-naphthalenedimethylene. Preferably, R1 is a C2-C16 aliphatic alkylene or a C8-C14 aromatic alkylene. The inventors have found that in this preferred embodiment, nylon products have higher dyeing uniformity and better dyeing stability.

[0048] As one preferred embodiment of the dye chromophore group, the structural formula of the dye chromophore group is at least one selected from formula (II), formula (III), and formula (IV).

[0049]

Chemical formula

[0050] Here, R I , R II , R III , R IV , and R V are each independently hydrogen and / or a water-soluble group, and p is an integer from 1 to 10. The inventors have found that in this preferred embodiment, colored nylon has higher dyeing uniformity and better product stability.

[0051] In the present invention, the water-soluble group may be any hydrophilic or water-soluble substituent. Preferably, the water-soluble group is -(CR VI R VII ) m’ -SO3M, where R VI , RVII Each of these is independently hydrogen and at least one selected from C1-C5 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl), and M is a monovalent metal ion and / or ammonium ion, preferably an alkali metal ion, more preferably Li + kaNa + or K + The present inventors have found that in this preferred embodiment, the color uniformity and stability of the colored nylon can be further improved.

[0052] In another preferred embodiment of the dye coloring group, the dye coloring group is preferably an anthraquinone group represented by formula (V) in an unsubstituted or substituted form.

[0053] [ka]

[0054] Here, the substituents of the anthraquinone group represented by formula (V) are substituents that do not contain terminal amino acids.

[0055] [ka]

[0056] It may be at least one selected from the above. The inventors have found that in this preferred embodiment, the uniformity and stability of the dyeing of the colored nylon can be further improved.

[0057] In this case, the dye monomers that provide the dye color group are 1-amino-2,4-dibromoanthraquinone, 1-amino-2-bromo-4-hydroxyanthraquinone, 2-amino-3-hydroxyanthraquinone, 2-amino-1-chloroanthraquinone, 1-amino-2-(4-bromophenoxy)-4-hydroxyanthraquinone, 1-amino-4-phenylamino-2-bromoanthraquinone, 1-amino-5-hydroxy-4-[(1-methylpropyl)amino]-8-nitro-9,10-anthraquinone, Acid Blue 129, Acid Blue 25, CI Disperse Red 60, Disperse Blue 359, 1-amino-4-nitroanthraquinone-2- Cyclohexyl carboxylate, Disperse Violet No. 4, 1-amino-5-benzoylaminoanthraquinone, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-amino-4-hydroxyanthraquinone, Acid Blue 40, 2-chloro-4-hydroxy-1-aminoanthraquinone, 1-bromo-3-chloro-2-aminoanthraquinone, 1-amino-4-bromo-2-methylanthraquinone, Disperse Violet 15, 1-amino-4-hydroxy-2-(phenylthio)anthraquinone, 1-amino-9,10-dihydro-4-[[(4-methylphenyl)sulfonyl]amino]-anthraquinone-2-sulfonic acid, CIReactive Blue 19, 1-amino-4-[(2-methoxyphenyl)amino]anthraquinone, 1-amino-5-hydroxy-4-[(4-methoxyphenyl)amino]-8-nitroanthraquinone, 1-amino-4-bromoanthraquinone-2-sulfonate sodium, 1-amino-4-bromoanthraquinone-2-sulfonic acid, 1-amino-2-bromo-4-[[3-(dimethylamino)propyl]amino]anthraquinone, 1-amino-4-hydroxy-2-[2-[4-(2-hydroxyethyl)phenyl]ethoxy]anthraquinone, 1-amino-4-bromoanthraquinone, 1-amino-4-hydroxy-2-(4-methoxyphenoxy)ant It is at least one selected from Laquinone, Disperse Red 86, Disperse Red 53, 2-amino-3-hydroxyanthraquinone, Disperse Orange 11, 1-amino-5-[(2,4-dibromophenyl)amino]-4,8-dihydroxyanthraquinone, 1-amino-4,5-dihydroxy-8-(methylamino)anthraquinone, Reactive Blue 4, 1-amino-4-hydroxy-2-[(2-hydroethyl)thio]anthraquinone, 1-amino-5-chloroanthraquinone, 1-amino-2-bromo-4-(3-chloroaniline)anthraquinone, Disperse Red E-4B, and 2-amino-3-chloroanthraquinone.

[0058] In another embodiment of the present invention, preferably, the condensate containing the dye color group contains two terminal aminos or two terminal carboxyls and has a structural unit a represented by formula (VI).

[0059] [ka]

[0060] (Here, R2 is an aliphatic alkylene or aromatic alkylene, and Q'' is the dye coloring group.) In the present invention, R2 may be any aliphatic alkylene, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, octylene, undecylene, or dodecylene, or any aromatic alkylene, such as terephthalylidene, phthalylidene, isophthalylidene, 1,3-naphthalenedimethylene, 1,4-naphthalenedimethylene, 1,5-naphthalenedimethylene, 1,7-naphthalenedimethylene, 2,6-naphthalenedimethylene, and 2,7-naphthalenedimethylene, preferably R2 is a C2-C16 aliphatic alkylene or a C8-C14 aromatic alkylene, more preferably a C8-C14 aromatic alkylene. The inventors have found that in this preferred embodiment, the nylon product has higher dye uniformity and better dye stability. According to the present invention, preferably, the dye color-developing group is a group represented by formula (VII) which is either unsubstituted or substituted, or a group represented by formula (VIII) which is either unsubstituted or substituted.

[0061] [ka]

[0062] [ka]

[0063] Here, the substituents of the group represented by formula (VII) and the substituents of the group represented by formula (VIII) are, independently, substituents that do not contain terminal amino acids and can be selected from the same substituents as the anthraquinone group represented by formula (V) above.

[0064] Examples of dye monomers that provide dye color groups include 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone, 1,2-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,8-diaminoanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, 1,4-diamino-2,3-dihydroxyanthraquinone, Disperse Red 11, Solvent Violet 59, 1,5-diamino-4,8-dihydroxyanthraquinone, CI Disperse Blue 56, Disperse Blue 56, 4,8-diamino-1,5-dihydroxy-2-(4-hydroxyphenyl)anthraquinone, and 1,5-diamino-4,8-dihydroxy(4 It is at least one selected from -methoxyphenyl)anthraquinone, 4,4-diamino-1,1-iminodianthaquinone, 1,1-iminobis(5-aminoanthraquinone), 4,8-diamino-2-bromo-1,5-dihydroxyanthraquinone, 1,4-diaminoanthraquinone-2,3-disulfonic acid, Disperse Violet 8, Disperse Blue 81, 1,5-diamino-2-bromo-4,8-dihydroxyanthraquinone, 1,5-diamino-4,8-dihydroxy(4-hydroxyphenyl)anthraquinone, 1,8-diamino-4,5-dihydroxyanthraquinone, and 1,2-diamino-3,4-dicyanoanthraquinone.

[0065] According to the present invention, preferably, the process for producing the condensate containing the dye chromogenic group includes a step of performing a reaction I with a dye monomer containing the dye chromogenic group and an excess amount of dibasic acid, and removing the unreacted dibasic acid. During this reaction, the residues of the dye chromogenic group and the dibasic acid are linked by an amide bond, and since the properties of the dye monomer, the dibasic acid, and the condensate containing the dye chromogenic group are completely different, the dibasic acid that does not participate in the reaction can be easily separated. Therefore, according to the method for producing colored nylon of the present invention, the subsequent wastewater does not contain dye, that is, the entire amount of dye is utilized, and the wastewater treatment process is simplified, which can save wastewater treatment costs.

[0066] NMR analysis was performed on the condensate containing the dye chromogenic group, the dye monomer, and the dibasic acid. For example, as shown in Figure 14, characteristic peaks of the dye and the dibasic acid were clearly observed in the condensate containing the dye chromogenic group. For example, the peak at chemical shift 12.02 ppm corresponds to the carboxyl group, multiple peaks at 8.0–6.5 ppm correspond to the hydrogen of the dye, the peak at 2.24–2.18 ppm corresponds to the hydrogen peak of the -CH2- adjacent to the carboxyl group of the dibasic acid, and the peak at 1.53–1.42 ppm corresponds to the hydrogen peak of the -CH2- in the central position of the dibasic acid. The peak area ratio of the two peaks is 1:2, indicating that in the reaction process between the dibasic acid and the dye monomer, only one carboxyl group reacted with the amino group of the dye monomer, while the carboxyl group at the other end was retained. Furthermore, liquid chromatography tests were performed on the condensate containing the dye chromogenic group, the dye monomer, and the dibasic acid. As shown in Figure 15, no dibasic acid was observed in the condensate containing the dye chromogenic group, indicating that the purification of the condensate was relatively successful. Unreacted dibasic acid can be sufficiently removed through purification methods such as solvent extraction, filtration, and drying, reducing its impact on subsequent colored nylon polymerization and enabling the full utilization of the dye.

[0067] According to the present invention, preferably, the dibasic acid is at least one selected from aliphatic C2-C16 dibasic acids and / or aromatic C8-C14 dibasic acids, preferably oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, terephthalic acid, phthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.

[0068] In the present invention, the dye monomer and the dibasic acid can be purchased commercially or produced by conventional manufacturing methods. According to the present invention, the molar ratio of the amount of dye monomer to the dibasic acid used may be set according to the type of dye monomer, the type of dibasic acid, etc. Preferably, the molar ratio of the dye monomer to the dibasic acid is 1:0.01 to 100, more preferably 1:2 to 50, and even more preferably 1:5 to 20. By using a significantly larger amount of a more inexpensive and readily available dibasic acid, the reaction rate of the dye monomer can be greatly improved, and the reaction rate of the dye can be made to about 100%.

[0069] According to the present invention, in one preferred form of reaction I, the process of reaction I includes mixing the dye monomer and the dibasic acid under oxygen-free conditions to sequentially carry out the first-stage reaction I and the second-stage reaction I.

[0070] In the present invention, oxygen-free conditions are obtained by conventional methods of the art, such as nitrogen introduction and / or vacuum suction.

[0071] According to the present invention, preferably, the conditions for the first step reaction I include at least a temperature of 200-250°C, a pressure of 0.08-0.12 MPa, and a time of 3-5 hours.

[0072] According to the present invention, preferably, the conditions for the second-stage reaction I include at least a temperature of 200 to 250°C, a pressure of -0.03 to -0.06 MPa, and a time of 2 to 10 hours.

[0073] In the present invention, after cooling the reaction solution obtained by the second-stage reaction I, a condensate containing a dye color-developing group can be obtained by extraction I and drying. The extractant I used in extraction I may be water or a common organic solvent, such as water, methanol, ethanol, or acetone. Preferably, the weight ratio of the dye monomer to the extractant I is 1:5 to 30.

[0074] In the present invention, a particularly preferred method for producing a condensate containing a dye color-developing group includes the steps of: mixing a dye monomer containing the dye color-developing group with a dibasic acid in a molar ratio of 1:2 to 50, introducing nitrogen for protection, and carrying out the reaction for 3 to 5 hours while stirring at a temperature of 215 to 250°C and a pressure of 0.08 to 0.12 MPa; vacuuming the mixture to a pressure of -0.03 to -0.06 MPa, continuing the reaction for 2 to 10 hours at a temperature of 215 to 250°C, terminating the reaction, cooling the reaction solution to room temperature, and obtaining a crude condensate product; and adding an extractant (weight ratio of dye monomer to extractant I is 1:5 to 30) to the crude condensate product, heating and stirring, solid-liquid separation, drying, and obtaining a condensate containing a dye color-developing group.

[0075] In the present invention, conventional separation methods such as filtration and centrifugal separation can be used for solid-liquid separation, and conventional separation methods such as vacuum drying and hot air drying can be used for drying.

[0076] For example, if the dye monomer is alcohol-soluble aniline black, the synthesis scheme for forming a dye condensate with a dibasic acid is as follows:

[0077] [ka]

[0078] When the aforementioned dye monomer is water-soluble aniline black, the synthesis scheme for forming a dye condensate with a dibasic acid is as follows.

[0079] [ka]

[0080] Here, R1 is -(CH2) a -,

[0081] [ka]

[0082] And a is an integer between 0 and 14.

[0083] When the dye monomer is 1,4-diaminoanthraquinone, according to a particularly preferred method for producing a condensate containing a dye color group, it is reacted with a dibasic acid in various ratios, and the synthesis scheme may be as follows.

[0084] [ka]

[0085] Here, R2 is -(CH2) n -,

[0086] [ka]

[0087] The expression is such that n is an integer between 1 and 14.

[0088] According to the present invention, in another preferred form of reaction I, the process of reaction I includes mixing the dye monomer and the dibasic acid to carry out reaction I to obtain a condensation salt, and then sequentially carrying out first-stage reaction II and second-stage reaction II on the condensation salt under oxygen-free conditions.

[0089] According to the present invention, preferably, the conditions for the mixed reaction I include at least a temperature of 50 to 70°C, a pressure of 0.08 to 0.12 MPa, and a time of 1 to 5 hours.

[0090] According to the present invention, preferably, the conditions for the first-stage reaction II include at least a temperature of 200-250°C, a pressure of 0.08-0.12 MPa, and a time of 1-5 hours.

[0091] According to the present invention, preferably, the conditions for the second-stage reaction II include at least a temperature of 200 to 250°C, a pressure of -0.04 to -0.09 MPa, and a time of 2 to 8 hours.

[0092] According to the present invention, preferably, the weight ratio of the condensate containing the dye coloring group to the nylon monomer is 1:50 to 3000, more preferably 1:50 to 1500.

[0093] In the present invention, the process of mixed reaction I is carried out in the presence of reaction solvent I. Specifically, methanol or ethanol may be used as reaction solvent I. The solvent is removed from the reaction solution obtained by mixed reaction I and dried to obtain the condensation salt. The condensation salt is then mixed with reaction solvent II, and the first-stage reaction II and the second-stage reaction II are carried out sequentially. Exemplarily, deionized water may be used as reaction solvent II, and the concentration of the condensation salt in the mixture obtained by mixing the condensation salt and reaction solvent II is 30 to 80 wt%. After filtering the reaction solution obtained by the second-stage reaction II, the precipitate is subjected to washing I to obtain a condensate containing dye color groups. The detergent I used in washing I may be water or a common organic solvent, such as water, methanol, or ethanol, and preferably the mass ratio of the dye monomer to the detergent I is 1:0.5 to 10.

[0094] In the present invention, a particularly preferred method for producing a second type of condensate containing a dye coloring group is to mix and dissolve a dibasic acid with reaction solvent I to obtain a dibasic acid solution, heat it to 50-70°C, weigh a dye monomer in a predetermined ratio and dissolve it in reaction solvent I (the molar ratio of dye monomer to dibasic acid is 1:2-50), add it dropwise to the dibasic acid solution, and after the dropwise addition is complete, keep it warm at a pressure of 0.08-0.12 MPa and allow the reaction to proceed for 1-5 hours, remove reaction solvent I by rotary evaporation, and dry to obtain a condensate salt. The process includes the steps of obtaining a condensate, mixing and dissolving the condensate salt with deionized water to obtain an aqueous solution of the condensate salt at a predetermined concentration (condensate salt concentration of 30-80 wt%), reacting under nitrogen conditions at a temperature of 200-250°C and a pressure of 0.08-0.12 MPa for 1-5 hours, continuing the reaction for 2-8 hours by vacuum suction to a pressure of -0.04--0.09 MPa, terminating the reaction, cooling the reaction solution to room temperature, filtering, washing the precipitate, and drying to obtain a condensate containing dye color-developing groups.

[0095] For example, if the dye monomer is 2,6-diaminoanthraquinone, a particularly preferred method for producing a condensate containing a dye chromogenic group may involve reacting it with a dibasic acid in various ratios, and the synthesis scheme may be as follows.

[0096] [ka]

[0097] or

[0098] [ka]

[0099] Here, R2 is -(CH2) n -,

[0100] [ka]

[0101] The expression is such that n is an integer between 1 and 14.

[0102] According to the present invention, the ratio of the amount of condensate containing the dye color-developing group to the nylon monomer used may be set according to factors such as the type of nylon monomer, the type of dye color-developing group, and the requirements for the intensity of the dyeing. For example, the weight ratio of the condensate containing the dye color-developing group to the nylon monomer is 1:50 to 3000, more preferably 1:50 to 1500, and even more preferably 1:100 to 200.

[0103] According to the present invention, the nylon monomer may be any monomeric substance for synthesizing nylon, and the monomeric substance for synthesizing nylon may be polymerized with an auxiliary means (at least one of ω-aminocarboxylic acid, ω-aminocarboxylic acid salt, and polyamine-polyacid mixture) to form the corresponding nylon.

[0104] In one preferred embodiment of the nylon monomer, the nylon monomer may be a lactam, preferably a C2-C20 lactam, more preferably at least one selected from caprolactam, undecane lactam, and lauryl lactam. In this case, the nylon monomer may contain at least one of ω-aminocarboxylic acid, ω-aminocarboxylic acid salt, and polyamine-polyacid mixture, where the ω-aminocarboxylic acid may be at least one selected from aminocaproic acid, aminoundecanoic acid, and aminododecanoic acid; the ω-aminocarboxylic acid salt is at least one selected from nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt, nylon 1313 salt, nylon 1012 salt, and nylon 1010 salt; the polyamine in the polyamine-polyacid mixture is at least one selected from ethylenediamine, hexamethylenediamine, decanediamine, and p-phenylenediamine; and the polyacid is at least one selected from oxalic acid, adipic acid, sebacic acid, and dodecanediic acid.

[0105] In the present invention, R2 may be any aliphatic alkylene, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, octylene, undecylene, or dodecylene, or any aromatic alkylene, such as terephthalylidene, phthalylidene, isophthalylidene, 1,3-naphthalenedimethylene, 1,4-naphthalenedimethylene, 1,5-naphthalenedimethylene, 1,7-naphthalenedimethylene, 2,6-naphthalenedimethylene, and 2,7-naphthalenedimethylene, preferably R2 is a C2-C16 aliphatic alkylene or a C8-C14 aromatic alkylene, more preferably a C8-C14 aromatic alkylene. The inventors have found that in this preferred embodiment, the nylon product has higher dye uniformity and better dye stability.

[0106] In another preferred embodiment of the nylon monomer, the nylon monomer is at least one selected from aliphatic nylon salts, preferably nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt, nylon 1313 salt, nylon 1012 salt, and nylon 1010 salt.

[0107] In the present invention, the nylon monomer may be obtained as a commercially available product or may be manufactured in-house by a conventional manufacturing method.

[0108] According to the present invention, when the nylon monomer is a lactam, the condensation reaction is carried out in the presence of an auxiliary agent, the auxiliary agent being an organic monobasic acid, and preferably when the nylon monomer is at least one selected from caprolactam, undecane lactam, and lauryl lactam, the auxiliary agent is an aliphatic monobasic acid and / or an aromatic monobasic acid, more preferably an aromatic monobasic acid, and even more preferably benzoic acid.

[0109] When the nylon monomer is a lactam, the condensation reaction system may contain at least one of ω-aminocarboxylic acid, ω-aminocarboxylic acid salts, and polyamine-polyacid mixtures, wherein the ω-aminocarboxylic acid is at least one selected from aminocaproic acid, aminoundecanoic acid, and aminododecanoic acid; the ω-aminocarboxylic acid salt is at least one selected from nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt, nylon 1313 salt, nylon 1012 salt, and nylon 1010 salt; the polyamine in the polyamine-polyacid mixture is at least one selected from ethylenediamine, hexamethylenediamine, decanediamine, and p-phenylenediamine; and the polyacid is at least one selected from oxalic acid, adipic acid, sebacic acid, and dodecanediic acid.

[0110] According to the present invention, preferably, the molar ratio of the terminal amino of the polyamine to the carboxy of the polyacid is 1:0.9 to 1.1.

[0111] In this case, more preferably, the condensation reaction includes a sequential ring-opening reaction, a first-stage reaction III, a second-stage reaction III, and a third-stage reaction I.

[0112] According to the present invention, preferably, the conditions for the ring-opening reaction include at least a temperature of 200 to 230°C, a pressure of 0.08 to 0.12 MPa, and a time of 0.5 to 1 hour.

[0113] According to the present invention, preferably, the conditions for the first-stage reaction III include at least a temperature of 240 to 270°C, a pressure of 0.6 to 1.5 MPa, and a time of 2 to 4 hours.

[0114] According to the present invention, preferably, the conditions for the second-stage reaction III include at least a temperature of 235 to 250°C, a pressure of 0.08 to 0.12 MPa, and a time of 0.5 to 1.5 hours.

[0115] According to the present invention, preferably, the conditions for the third-stage reaction I include at least a temperature of 235 to 250°C, a pressure of -0.05 to -0.09 MPa, and a time of 1 to 3 hours.

[0116] Exemplaryly, in the present invention, a particularly preferred method for producing a first type of colored nylon involves mixing a condensate containing a dye coloring group, lactam, benzoic acid, and deionized water (the weight ratio of the condensate to lactam is 1:50 to 2000, preferably 1:50 to 200, the weight ratio of deionized water to lactam is 1:20 to 100, and the molar ratio of benzoic acid to lactam is 1:50 to 300), replacing the air in the system by repeating vacuum suction and nitrogen introduction three times, and heating at a temperature of 200 to 230°C. The process includes the steps of: reacting for 0.5 to 1 hour under conditions of °C and a pressure of 0.08 to 0.12 MPa to carry out the ring-opening reaction of the lactam; then further raising the temperature to 240 to 270 °C and controlling the system pressure to 0.6 to 1.5 MPa for 2 to 4 hours; cooling the temperature to 235 to 250 °C and releasing the pressure in the system; then continuing the reaction for 0.5 to 1.5 hours under conditions of a pressure of 0.08 to 0.12 MPa; and finally, using vacuum suction to control the system pressure to -0.05 to -0.09 MPa for 1 to 3 hours to obtain the reaction solution and cooling the reaction melt. According to the present invention, when the nylon monomer is an aliphatic nylon salt, the auxiliary agent is an organic dibasic acid, and preferably the nylon monomer is nylon 66 salt (hexamethylenediamine adipate salt), nylon 610 salt (hexamethylenediamine sebacate salt), nylon 612 salt (hexamethylenediamine dodecanediate salt), nylon 56 salt (pentamethylenediamine adipate salt), nylon 512 salt (pentamethylenediamine dodecanediate salt), nylon 1212 The salt is at least one selected from dodecanediamine dodecanediate, nylon 1313 salt (tridecamethylenediamine tridecanediate), nylon 1012 salt (decanediamine dodecanediate), and nylon 1010 salt (decanediamine sebacate), and the condensation reaction is carried out in the presence of an auxiliary agent, the auxiliary agent being an organic dibasic acid, preferably an aliphatic dibasic acid and / or an aromatic dibasic acid, more preferably an aliphatic dibasic acid, and even more preferably an adipic acid.

[0117] In this case, more preferably, the condensation reaction includes a first-stage reaction IV and a second-stage reaction IV, which are carried out sequentially.

[0118] According to the present invention, preferably, the conditions for the first-step reaction IV include at least a temperature of 180-230°C, a pressure of 1-1.8 MPa, and a time of 2-4 hours.

[0119] According to the present invention, preferably, the conditions for the second-stage reaction IV include at least a temperature of 240 to 270°C, a pressure of -0.05 to -0.09 MPa, and a time of 1 to 3 hours.

[0120] According to the present invention, preferably, the pressure release time for the first-stage reaction IV is 1 to 1.5 hours.

[0121] Exemplary, in the present invention, a particularly preferred method for producing a second type of nylon product includes the steps of: mixing a condensate containing a dye coloring group, an aliphatic nylon salt, adipic acid, and deionized water (the weight ratio of the dye condensate to the nylon monomer is 1:50 to 3000, the weight ratio of the deionized water to the nylon monomer is 1:5 to 50, and the molar ratio of the adipic acid to the nylon monomer is 1:30 to 200); replacing the air in the system by repeating vacuum suction and nitrogen introduction three times; reacting for 2 to 4 hours under conditions of a temperature of 200 to 230°C and a pressure of 1 to 1.8 MPa; then releasing the pressure in the system to atmospheric pressure, controlling the pressure release time to 1 to 1.5 hours; further raising the temperature to 240 to 270°C; vacuum suction to a pressure of -0.05 to -0.09 MPa; reacting for 1 to 3 hours to obtain a reaction solution; and cooling the reaction melt.

[0122] According to the present invention, the molar ratio of the nylon monomer to the auxiliary agent may be set according to factors such as the type of nylon monomer and the molecular weight of the resulting colored nylon polymer. Preferably, the molar ratio of the nylon monomer to the auxiliary agent is 30 to 350:1, more preferably 50 to 320:1, and even more preferably 90 to 320:1. In this preferred case, the reaction efficiency between the nylon polymerization system and the condensate containing the dye coloring group can be effectively improved.

[0123] In the present invention, a condensate containing a dye coloring group, a nylon monomer, and an auxiliary agent are subjected to a condensation reaction in a reaction solvent, and deionized water may be used as the reaction solvent. The weight ratio of the reaction solvent to the nylon monomer is preferably 1:5 to 100. The condensation reaction of colored nylon can be carried out effectively even when a relatively small amount of deionized water is used, the proportion of the reaction solvent used is small compared to the nylon monomer, and furthermore, the deionized water volatilizes under the high-temperature reaction conditions required for the condensation reaction, so that the melt obtained by the condensation reaction can be cooled and directly used in processing steps for nylon products such as slicing.

[0124] The method of the present invention can be considered as a combination of two processes: nylon manufacturing and dyeing. Compared to the conventional process of manufacturing nylon first and then dyeing it, the method of the present invention is simpler, easier to implement, and the resulting colored nylon has high colorfastness and high color uniformity. The degree of dyeing can be controlled over a wide range by controlling the amount of dye added. Compared to the conventional technique of manufacturing nylon by steaming amine dyes, diamines, and dibasic acids or dicarboxylic acid halides in one pot, increasing the amount of dibasic acid added allows for complete reaction of the amine dye, thereby improving the utilization rate of the dye. Furthermore, by utilizing the fact that condensation polymers, amine dyes, and dibasic acids have significantly different properties and are easily separated, unreacted dibasic acids can be separated, purified, and recycled, enabling the complete utilization of the amine dye and avoiding the discharge of dye-containing wastewater.

[0125] A third aspect of the present invention provides colored nylon manufactured by the manufacturing method described above.

[0126] In the present invention, the colored nylon obtained by the above-described manufacturing method can be processed into materials such as fibers by performing processes such as slicing, spinning, or winding as needed. A fourth aspect of the present invention provides the use of the above-described colored nylon in at least one of spinning, industrial fibers, and engineering materials.

[0127] The present invention will be described in detail below with reference to examples.

[0128] In the following examples and comparative examples, the test process for steaming colored nylon in an organic solvent is as follows: After mixing colored nylon and ethyl acetate in a weight ratio of 1:3, the mixture is refluxed at 77°C for 24 hours, filtered to remove solid colored nylon, and then the presence or absence of a change in the color of the ethyl acetate supernatant is observed. The chromaticity of the ethyl acetate supernatant after steaming is measured according to HJ 1182-2021 "Water Quality - Measurement of Chromaticity: Dilution Factor Method". Water colorfastness is measured according to the international standard ISO 105-E01, sweat colorfastness is measured according to the international standard ISO 105-E04, and soap wash colorfastness is measured according to the international standard ISO 105-C10.

[0129] The process for detecting the halogen ion content in a boiled solution of colored nylon is as follows: Colored nylon and deionized water are mixed in a 1:1 weight ratio, and the mixture is steamed at 100°C for 3 hours to obtain a boiled solution. This boiled solution is then sampled, and the halogen ion concentration is measured by ion chromatography.

[0130] The dyeing uniformity effect characterizes the difference in color intensity (Sr): The process for testing these is as follows: The difference in dyeing color intensity is expressed using the standard deviation of K / S values ​​(ΔK / S) from multiple tests. K / S values ​​were measured at various positions on a 10cm x 10cm, 3mm thick nylon slice using a Datacolor 850 colorimeter (eight measurement points were selected along two diagonals and two long sides for each slice). The K / S values ​​were used as sample data, and the difference in color intensity expressed in Sr was obtained by calculating its standard deviation (ΔK / S).

[0131] Unless otherwise specified, the raw materials and reagents used are conventional commercially available products.

[0132] Unless otherwise specified, normal pressure refers to 1 atmosphere (approximately 0.1 MPa).

[0133] Manufacturing Example 1 Alcohol-soluble aniline black (structural formula is

[0134] [ka]

[0135] 10.0 g of p(1) and 125 g of succinic acid were sequentially added to the reactor and heated to 220°C under a nitrogen atmosphere for 3 hours. The reaction was continued at 220°C for 7 hours under vacuum suction to -0.04 MPa, stirring was stopped, the reaction solution was poured into a 250 ml beaker, cooled to room temperature, 100 ml of water was added to the beaker, heated and stirred to extract, filtered and dried to obtain carboxy-containing dye condensate 1-1. The structural formula of the dye condensate 1-1 is shown in Table 1, and the infrared spectral data is as follows: 3100~3000 cm⁻¹ -1 This corresponds to the =CH- stretching vibration peak on the benzene ring of aniline black, at wavenumbers 2939-2859 cm⁻¹. -1 There are two absorption peaks between them, corresponding to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3303 cm⁻¹. -1 The absorption peak at wavenumber 1643 cm corresponds to the NH stretching vibration of the amide bond. -1 This corresponds to the absorption peak of carboxyl, at 1588 cm⁻¹. -1 A characteristic peak of carbon-nitrogen double bonds can be seen in the vicinity, at 1487–1460 cm⁻¹. -1 A characteristic peak of cyclohexadienyl is observed in the vicinity, and the infrared spectra of the dye monomer, dibasic acid, and dye condensate 1-1 in Production Example 1 are shown in Figure 1.

[0136] Manufacturing Example 2 Water-soluble aniline black (structural formula is

[0137] [ka]

[0138] 10 g of p(1) and 87.5 g of adipic acid were sequentially added to the reactor and heated to 230°C under a nitrogen atmosphere for 3 hours. Vacuum suction was reduced to -0.06 MPa, and the reaction was continued at 230°C for 5.5 hours. After stopping the stirring, the reaction solution was poured into a 250 ml beaker and cooled to room temperature. 100 ml of methanol was added to the beaker, heated and stirred to extract the solution, then filtered and dried to obtain carboxy-containing dye condensate 1-2. The structural formula of dye condensate 1-2 is shown in Table 1, and the infrared spectral data is as follows: 3150~3010 cm⁻¹ -1 This corresponds to the =CH- stretching vibration peak on the benzene ring of aniline black, with wavenumbers 2945-2850 cm⁻¹. -1 There are two absorption peaks in between, corresponding to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3310 cm⁻¹. -1 The absorption peak corresponds to the NH stretching vibration on the amide bond, at wavenumber 1650 cm⁻¹. -1 This corresponds to the absorption peak of carboxyl, at 1590 cm⁻¹. -1 A characteristic peak of carbon-nitrogen double bonds can be seen in the vicinity, at 1492–1450 cm⁻¹. -1 A characteristic peak of cyclohexadienyl can be seen in the vicinity.

[0139] The NMR analyses of the dye condensate, dye monomer, and dibasic acid in Production Example 2 are shown in Figure 14, and the liquid chromatography tests of the dye condensate, dye monomer, and dibasic acid are shown in Figure 15.

[0140] Manufacturing Example 3 Water-soluble aniline black (structural formula is

[0141] [ka]

[0142] 10g of p(2) and 58.5g of sebacic acid were sequentially added to the reactor and heated to 235°C under a nitrogen atmosphere for 3 hours. The reaction was carried out under vacuum suction to -0.04 MPa and continued at 235°C for 7 hours. After stopping the stirring, the reaction solution was poured into a 250 ml beaker and cooled to room temperature. 100 ml of ethanol was added to the beaker, heated and stirred to extract the solution, then filtered and dried to obtain carboxy-containing dye condensate 1-3. The structural formula of dye condensate 1-3 is shown in Table 1, and the infrared spectral data is as follows: 3200~3020 cm⁻¹ -1 This corresponds to the =CH- stretching vibration peak on the benzene ring of aniline black, with wavenumbers 2905-2810 cm⁻¹. -1 There are two absorption peaks between them, corresponding to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3302 cm⁻¹. -1 The absorption peak at wavenumber 1652 cm corresponds to the NH stretching vibration on the amide bond. -1 This corresponds to the absorption peak of carboxyl, at 1591 cm⁻¹. -1 A characteristic peak of carbon-nitrogen double bonds can be seen in the vicinity, at 1496–1457 cm⁻¹. -1 A characteristic peak of cyclohexadienyl can be seen in the vicinity.

[0143] Manufacturing Example 4 Dye monomer (structural formula is

[0144] [ka]

[0145] 10g of p(2) and 58.5g of sebacic acid were sequentially added to the reactor and heated to 235°C under a nitrogen atmosphere for 3 hours. The reaction was carried out under vacuum suction to -0.04 MPa and continued at 235°C for 7 hours. After stopping the stirring, the reaction solution was poured into a 250 ml beaker and cooled to room temperature. 100 ml of ethanol was added to the beaker, heated and stirred to extract the solution, then filtered and dried to obtain carboxy-containing dye condensate 1-4. The structural formula of dye condensate 1-4 is shown in Table 1, and the infrared spectral data is as follows: 3210~3010 cm⁻¹ -1This corresponds to the =CH- stretching vibration peak on the benzene ring of aniline black, with wavenumbers 2950-2840 cm⁻¹. -1 There are two absorption peaks between them, corresponding to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3315 cm⁻¹. -1 The absorption peak at wavenumber 1658 cm corresponds to the NH stretching vibration on the amide bond. -1 This corresponds to the absorption peak of carboxyl, at 1595 cm⁻¹. -1 A characteristic peak of carbon-nitrogen double bonds can be seen in the vicinity, at 1495–1445 cm⁻¹. -1 A characteristic peak of cyclohexadienyl can be seen in the vicinity.

[0146] Manufacturing Example 5 Acid Blue 260 (Structural formula is

[0147] [ka]

[0148] 10g of ) and 32.0g of succinic acid were sequentially added to the reactor and heated to 220°C under a nitrogen atmosphere for 3 hours. Vacuum suction was reduced to -0.04 MPa, and the reaction was continued at 220°C for 7 hours. Stirring was stopped, the reaction solution was poured into a 250 ml beaker, cooled to room temperature, 100 ml of water was added to the beaker, and after heating and extraction, the mixture was filtered and dried to obtain carboxy-containing dye condensate 1-5. The structural formula of dye condensate 1-5 is shown in Table 1, and the infrared spectral data is as follows: Wavenumber 3100~3000 cm -1 The small absorption peak observed corresponds to the =CH- stretching vibration peak of the anthraquinone ring, at wavenumbers 2900–2750 cm⁻¹. -1 The absorption peak in between corresponds to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3260 cm⁻¹. -1 The absorption peak corresponds to the NH stretching vibration of the amide bond.

[0149] Manufacturing Example 6 10 g of Acid Blue 260 (structural formula the same as in Production Example 5) and 39 g of adipic acid were sequentially added to a reactor and heated to 230°C under a nitrogen atmosphere for 3.0 hours. The reaction was continued at 230°C for 7 hours under vacuum suction to -0.04 MPa, stirring was stopped, the reaction solution was poured into a 250 ml beaker, cooled to room temperature, 100 ml of methanol was added to the beaker, and after heating and extraction, the mixture was filtered and dried to obtain carboxy-containing dye condensate 1-6. The structural formula of dye condensate 1-6 is shown in Table 1, and the infrared spectral data is as follows: wavenumber 3100~3000 cm -1 The small absorption peak observed corresponds to the =CH- stretching vibration peak of the anthraquinone ring, at wavenumbers 2920–2760 cm⁻¹. -1 The absorption peak in between corresponds to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3250 cm⁻¹. -1 The absorption peak corresponds to the NH stretching vibration of the amide bond.

[0150] Manufacturing example 7 10 g of Acid Blue 260 (structural formula the same as in Production Example 5) and 54 g of sebacic acid were sequentially added to a reactor and heated to 235°C under a nitrogen atmosphere for 3 hours. The reaction was carried out under vacuum suction to -0.04 MPa and continued at 235°C for 7 hours. After stopping the stirring, the reaction solution was poured into a 250 ml beaker and cooled to room temperature. 100 ml of ethanol was added to the beaker, and after heating and extraction, the mixture was filtered and dried to obtain carboxy-containing dye condensate 1-7. The structural formula of dye condensate 1-7 is shown in Table 1, and the infrared spectral data is as follows: Wavenumber 3100~3000 cm -1 The small absorption peak observed corresponds to the =CH- stretching vibration peak of the anthraquinone ring, at wavenumbers 2930–2780 cm⁻¹. -1 The absorption peak in between corresponds to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3270 cm⁻¹. -1 The absorption peak corresponds to the NH stretching vibration of the amide bond.

[0151] Manufacturing Example 8 The structural formula of alcohol-soluble aniline black

[0152] [ka]

[0153] Except for changing (p to 1), the dye condensate was prepared according to the method of Example 1 to obtain carboxy-containing dye condensate 1-8. The structural formula of dye condensate 1-8 is shown in Table 1, and the infrared spectral data is as follows: 3150~3010 cm -1 This corresponds to the =CH- stretching vibration peak on the benzene ring of aniline black, with wavenumbers 2945-2850 cm⁻¹. -1 There are two absorption peaks between them, corresponding to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3315 cm⁻¹. -1 The absorption peak corresponds to the NH stretching vibration on the amide bond, at wavenumber 1650 cm⁻¹. -1 This corresponds to the absorption peak of carboxyl, at 1595 cm⁻¹. -1 A characteristic peak of carbon-nitrogen double bonds can be seen in the vicinity, at 1495–1455 cm⁻¹. -1 A characteristic peak of cyclohexadienyl can be seen in the vicinity.

[0154] Manufacturing Example 9 The structural formula of water-soluble aniline black

[0155] [ka]

[0156] Except for the change made, the dye condensate was prepared according to the method of Example 2 to obtain carboxy-containing dye condensate 1-9. The structural formula of dye condensate 1-9 is shown in Table 1, and the infrared spectral data is as follows: 3150~3010 cm⁻¹ -1 This corresponds to the =CH- stretching vibration peak on the benzene ring of aniline black, with wavenumbers 2945-2850 cm⁻¹. -1 There are two absorption peaks in between, corresponding to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3310 cm⁻¹. -1 The absorption peak at wavenumber 1652 cm corresponds to the NH stretching vibration on the amide bond. -1 This corresponds to the absorption peak of carboxyl, at 1593 cm⁻¹.-1 A characteristic peak of carbon-nitrogen double bonds can be seen in the vicinity, at 1497–1452 cm⁻¹. -1 A characteristic peak of cyclohexadienyl can be seen in the vicinity.

[0157] Manufacturing Example 10 The structural formula of Acid Blue 260

[0158] [ka]

[0159] Except for the change made, the dye condensate was prepared according to the method of Example 5 to obtain carboxy-containing dye condensate 1-10. The structural formula of dye condensate 1-10 is shown in Table 1, and the infrared spectral data is as follows: wavenumber 3100~3000 cm -1 The small absorption peak observed corresponds to the =CH- stretching vibration peak of the anthraquinone ring, at wavenumbers 2935–2765 cm⁻¹. -1 The absorption peak in between corresponds to the -CH2-stretching vibration peak of the fatty acid chain, at wavenumber 3270 cm⁻¹. -1 The absorption peak corresponds to the NH stretching vibration of the amide bond.

[0160] Manufacturing Example 11 Dye condensates 1-3 were prepared according to the method of Example 3, except that the reaction process was modified to involve heating to 215°C under a nitrogen atmosphere for 5 hours, vacuum suction to -0.03 MPa, sustaining the reaction at 215°C for 10 hours, stopping the stirring, pouring the reaction solution into a 250 ml beaker, cooling to room temperature, adding 100 ml of ethanol to the beaker, heating and stirring for extraction, followed by filtration and drying. Carboxylate-containing dye condensates 1-3 were obtained.

[0161] Manufacturing Example 12 Dye condensate 1-3 was prepared according to the method of Example 3, except that the reaction process was modified to involve heating to 250°C under a nitrogen atmosphere for 3 hours, vacuum suction to -0.06 MPa, continuing the reaction at 250°C for 4 hours, stopping stirring, pouring the reaction solution into a 250 ml beaker, cooling to room temperature, adding 100 ml of ethanol to the beaker, heating and stirring for extraction, followed by filtration and drying. Carboxylate-containing dye condensate 1-3 was obtained.

[0162] Manufacturing Example 13 Dye condensate 1-3 was produced according to the method of Example 3, except that the reaction process was modified to involve heating to 200°C under a nitrogen atmosphere for 3 hours, vacuum suction to -0.06 MPa, continuing the reaction at 200°C for 4 hours, stopping stirring, pouring the reaction solution into a 250 ml beaker, cooling to room temperature, adding 100 ml of ethanol to the beaker, heating and stirring for extraction, followed by filtration and drying. Carboxylate-containing dye condensate 1-3 was obtained.

[0163] Manufacturing Example 14 The structural formula of alcohol-soluble aniline black

[0164] [ka]

[0165] Except for the change to (acid black), the dye condensate was prepared according to the method of Production Example 1 to obtain carboxy-containing dye condensate 1-11. The structural formula of dye condensate 1-11 is shown in Table 1.

[0166] [Table 1] JPEG2026508820000027.jpg227169

[0167] Example 1 1500 g of caprolactam, 8.1 g of benzoic acid, 10.82 g of dye condensate 1-1 prepared in Production Example 1, and 68.2 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 mins, followed by vacuum suction for 10 mins. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 230°C, and the ring-opening reaction was carried out for 0.5 hours under atmospheric pressure and stirring conditions of 400 rpm. Subsequently, the temperature was further raised to 250°C, and the system pressure was controlled to 1.5 MPa by removing excess water, and the reaction was continued for 2.5 hours. The temperature was lowered to 240°C, the system pressure was released, and the reaction was continued at atmospheric pressure for 1.0 hour. Vacuum suction was applied until the system pressure reached -0.09 MPa, and after 1.5 hours of reaction, the reaction was stopped. The material was removed, cooled, and sliced ​​to obtain a black nylon-6 polymer.

[0168] The infrared spectra of dye condensate 1-1, caprolactam, and black nylon-6 in Example 1 are shown in Figure 2.

[0169] Example 2 1100 g of nylon-66 salt, 4.82 g of adipic acid, 6.25 g of dye condensate 1-2 prepared in Production Example 2, and 58.9 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 mins, followed by vacuum suction for 10 mins. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 215°C, and stirring was started at a stirring speed of 450 rpm. The system pressure was maintained at 1.7 MPa by removing water from the system, and the reaction was carried out at a constant temperature for 2.5 hours. After that, the system pressure was released to atmospheric pressure (pressure release time was approximately 1.5 hours). Finally, the temperature was further increased to 265°C, and the system pressure was vacuum suctioned until it reached -0.08 MPa. The reaction was continued for 2 hours, the reaction was stopped, the stirrer was stopped, the melt in the reaction vessel was poured out, cooled to room temperature, and sliced ​​to obtain a black nylon-66 polymer.

[0170] Example 3 1700g of nylon-1010 salt, 6.64g of adipic acid, 15.7g of dye condensate 1-3 prepared in Production Example 3, and 250ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by vacuum suction for 10 minutes. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 210°C, and stirring was started at a stirring speed of 450 rpm. The system pressure was maintained at 1.55 MPa by removing water from the system, and the reaction was carried out at a constant temperature for 3 hours. After that, the system pressure was released to atmospheric pressure (pressure release time was approximately 1 hour). Finally, the temperature was further increased to 260°C, and the system pressure was vacuum suctioned until it reached -0.08 MPa. The reaction was continued for 2 hours, the reaction was stopped, the stirrer was stopped, the melt in the reaction vessel was poured out, cooled to room temperature, and sliced ​​to obtain black nylon-1010 polymer.

[0171] Example 4 1530 g of nylon-612 salt, 6.58 g of adipic acid, 12.8 g of dye condensate 1-1 prepared in Production Example 1, and 102.0 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 mins, followed by vacuum suction for 10 mins. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 220°C, and stirring was started at a stirring speed of 450 rpm. The system pressure was maintained at 1.80 MPa by removing water from the system, and the reaction was allowed to proceed at a constant temperature for 2 hours. After that, the system pressure was released to atmospheric pressure (pressure release time was approximately 1.5 hours). Finally, the temperature was further increased to 270°C, and the system pressure was vacuum suctioned until it reached -0.06 MPa. The reaction was continued for 3 hours, the reaction was stopped, the stirrer was stopped, the melt in the reaction vessel was poured out, cooled to room temperature, and sliced ​​to obtain a black nylon-612 polymer.

[0172] Example 5 A black nylon-612 polymer was produced according to the method of Example 4, except that dye condensate 1-1 produced in Production Example 1 was replaced with dye condensate 1-4 produced in Production Example 4.

[0173] Example 6 A black nylon-6 polymer was produced according to the method of Example 1, except that dye condensate 1-1 produced in Production Example 1 was replaced with dye condensate 1-5 produced in Production Example 5.

[0174] Example 7 Black nylon-66 polymer was produced according to the method of Example 2, except that dye condensate 1-2 produced in Production Example 2 was replaced with dye condensate 1-6 produced in Production Example 6.

[0175] Example 8 Black nylon-1010 polymer was produced according to the method of Example 3, except that dye condensate 1-3 produced in Production Example 3 was replaced with dye condensate 1-7 produced in Production Example 7.

[0176] Example 9 Black nylon-612 polymer was produced according to the method of Example 4, except that dye condensate 1-1 produced in Production Example 1 was replaced with dye condensate 1-8 produced in Production Example 8.

[0177] Example 10 Black nylon-612 polymer was produced according to the method of Example 4, except that dye condensate 1-1 produced in Production Example 1 was replaced with dye condensate 1-9 produced in Production Example 9.

[0178] Example 11 Black nylon-1010 polymer was produced according to the method of Example 3, except that dye condensates 1-3 produced in Production Example 3 were replaced with dye condensate 1-10 produced in Production Example 10.

[0179] Example 12 Black nylon-612 polymer was produced according to the method of Example 4, except that dye condensate 1-1 produced in Production Example 1 was replaced with dye condensate 1-3 produced in Production Example 11.

[0180] Example 13 Black nylon-612 polymer was produced according to the method of Example 4, except that dye condensate 1-1 produced in Production Example 1 was replaced with dye condensate 1-3 produced in Production Example 12.

[0181] Example 14 Black nylon-612 polymer was produced according to the method of Example 4, except that dye condensate 1-1 produced in Production Example 1 was replaced with dye condensate 1-3 produced in Production Example 13.

[0182] Example 15 A black nylon-612 polymer was produced according to the method of Example 4, except that dye condensate 1-1 produced in Production Example 1 was replaced with dye condensate 1-11 produced in Production Example 14.

[0183] Example 16 Black nylon-6 polymer was produced according to the method of Example 1, except that the reaction process was modified as follows: Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by vacuum suction for 10 minutes, and this was repeated three times to completely remove the air from the vessel. The temperature was raised to 250°C, and the ring-opening reaction was carried out for 0.5 hours under conditions of a rotation speed of 400 rpm and a pressure of 0.15 MPa. Then, the temperature was further raised to 270°C, and the pressure of the system was controlled to 1.5 MPa by removing excess water, and the reaction was continued for 2 hours. The temperature was lowered to 250°C, the pressure of the system was released, and the reaction was continued at atmospheric pressure for 0.5 hours. Vacuum suction was applied until the pressure of the system became -0.09 MPa, and after 1 hour of reaction, the reaction was stopped, the material was removed, cooled, and sliced ​​to obtain black nylon-6 polymer.

[0184] Example 17 Black nylon-6 polymer was produced according to the method of Example 1, except that the reaction process was modified as follows: Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by vacuum suction for 10 minutes, and this was repeated three times to completely remove the air from the vessel. The temperature was raised to 200°C, and the ring-opening reaction was carried out for 0.5 hours under atmospheric pressure and stirring conditions at a rotation speed of 400 rpm. Then, the temperature was further raised to 220°C, and the pressure of the system was controlled to 1.8 MPa by removing excess water, and the reaction was continued for 2.5 hours. The temperature was lowered to 200°C, the pressure of the system was released, and the reaction was continued at atmospheric pressure for 1.5 hours. Vacuum suction was applied until the pressure of the system became -0.09 MPa, and after 1.5 hours of reaction, the reaction was stopped, the material was removed, cooled, and sliced ​​to obtain black nylon-6 polymer.

[0185] Example 18 Black nylon-6 polymer was produced according to the method of Example 1, except that the reaction process was modified as follows: Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by vacuum suction for 10 minutes, and this was repeated three times to completely remove the air from the vessel. The temperature was raised to 230°C, and the ring-opening reaction was carried out for 0.5 hours under atmospheric pressure and stirring conditions at 400 rpm. Then, the temperature was further raised to 265°C, and the pressure of the system was controlled to 1.5 MPa by removing excess water, and the reaction was carried out for 2.5 hours. The temperature was lowered to 220°C, the pressure of the system was released, and the reaction was continued at atmospheric pressure for 1.0 hour. Vacuum suction was applied until the pressure of the system became -0.02 MPa, and after 1.5 hours of reaction, the reaction was stopped, the material was removed, cooled, and sliced ​​to obtain black nylon-6 polymer.

[0186] Example 19 Black nylon-612 polymer was produced according to the method of Example 4, except that the reaction process was modified as follows: Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by vacuum suction for 10 minutes, and this was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 245°C, and stirring was started at a stirring speed of 450 rpm. The system pressure was maintained at 2.00 MPa by removing water from the system, and the reaction was carried out at a constant temperature for 2 hours. After that, the system pressure was released to atmospheric pressure (pressure release time was approximately 1.5 hours). Finally, the temperature was further increased to 270°C, and the system pressure was vacuum suctioned until it reached -0.06 MPa. The reaction was continued for 3 hours, the reaction was stopped, the stirrer was stopped, the melt in the reaction vessel was poured out, cooled to room temperature, and sliced ​​to obtain the black nylon-612 polymer.

[0187] Example 20 Black nylon-612 polymer was produced according to the method of Example 4, except that the reaction process was modified as follows: Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by vacuum suction for 10 minutes, and this was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 220°C, and stirring was started at a stirring speed of 450 rpm. The system pressure was maintained at 1.80 MPa by removing water from the system, and the reaction was carried out at a constant temperature for 2 hours. After that, the system pressure was released to atmospheric pressure (pressure release time was approximately 1.5 hours). Finally, the temperature was further increased to 230°C, and the system pressure was vacuum suctioned until it reached -0.02 MPa, and the reaction was continued for 3 hours. The reaction was then stopped, the stirrer was stopped, the melt in the reaction vessel was poured out, cooled to room temperature, and sliced ​​to obtain the black nylon-612 polymer.

[0188] Example 21 A black nylon-6 polymer was produced according to the method of Example 1, except that the amount of benzoic acid used was changed to 5 g.

[0189] Example 22 A black nylon-6 polymer was produced according to the method of Example 1, except that the amount of dye condensate 1-1 used was changed to 5 g.

[0190] Example 23 Black nylon-66 polymer was produced according to the method of Example 2, except that the amount of nylon-66 salt used was changed to 3000g and the amount of dye condensate 1-2 used was changed to 2.5g.

[0191] Example 24 1530 g of poly(p-phenylene terephthalamide) (PPTA monomer), 12.8 g of dye condensate 1-1 prepared in Production Example 1, and 102 mL of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 mins, followed by vacuum suction for 10 mins. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 220°C, and stirring was started at a stirring speed of 450 rpm. The system pressure was maintained at 1.80 MPa by removing water from the system, and the reaction was carried out at a constant temperature for 2 hours. After that, the system pressure was released to atmospheric pressure (pressure release time was approximately 1.5 hours). Finally, the temperature was further increased to 270°C, and the system pressure was vacuum suctioned until it reached -0.06 MPa. The reaction was continued for 3 hours, the reaction was stopped, the stirrer was stopped, the melt in the reaction vessel was poured out, cooled to room temperature, and sliced ​​to obtain a black aromatic nylon product.

[0192] Comparative Example 1 Nylon-6 was dyed by immersion dyeing using alcohol-soluble aniline black as the dye. The specific process was as follows: the dye molecules were supplied to a belt, placed in a colored tank, steamed with a hot steamer, rinsed with water, baked, and removed from the belt, allowing the dye molecules to react sufficiently with the corresponding functional groups of nylon-6. Finally, the dye molecules that had not reacted completely were removed and thoroughly decomposed by rinsing with water and baking to obtain black nylon.

[0193] Comparative Example 2 Black nylon was manufactured according to the method of Comparative Example 1, except that nylon 6 was changed to nylon-66.

[0194] Comparative Example 3 Black nylon was manufactured according to the method of Comparative Example 1, except that nylon 6 was replaced with nylon-1010.

[0195] Comparative Example 4 Black nylon was manufactured according to the method of Comparative Example 1, except that nylon 6 was replaced with nylon-612.

[0196] Comparative Example 5 106 parts by weight of metaphenylenediamine and 4.8 parts by weight of 1,5-diaminoanthraquinone were dissolved in 950 parts by weight of dimethylacetamide. The solution was cooled to at least 25°C, 203 parts by weight of isophthaloyl chloride solution was added, and the temperature was raised to 40-45°C, gradually thickening the solution. The solution was then cooled to room temperature in an ice bath and stirred at this temperature for several hours. 10 parts by weight of calcium carbonate and 104 parts by weight of propylene oxide were used to remove the hydrochloric acid formed during the reaction, and the solution was then dried and sliced.

[0197] The nylon slices produced in Comparative Example 5 had a halogen ion content of 154 ppm in the boiling solution.

[0198] Comparative Example 6 106 parts by weight of 1,6-hexamethylenediamine and 4.8 parts by weight of 1,5-diaminoanthraquinone were dissolved in 950 parts by weight of dimethylacetamide. The solution was cooled to at least 25°C, 203 parts by weight of adipic acid chloride solution was added, and the temperature was raised to 40-45°C, gradually thickening the solution. The solution was then cooled to room temperature in an ice bath and stirred at this temperature for several hours. Hydrochloric acid formed during the reaction was removed using 10 parts by weight of calcium carbonate and 104 parts by weight of propylene oxide, and the solution was then dried and sliced.

[0199] The nylon slices produced in Comparative Example 6 had a halogen ion content of 342 ppm in the boiling solution.

[0200] Comparative Example 7 The commercially available black nylon-6, black nylon-66, black nylon-1010, black nylon-612, blue nylon-6, and blue nylon-1010 were all purchased from Guangzhou Chemical City Co., Ltd.

[0201] Test Example 1 Table 2 shows the results of determining the content of color-developing structural units by detecting them using nuclear magnetic resonance spectroscopy and infrared spectroscopy for the colored nylon slices produced in Examples 1 to 24 and the colored nylon provided in Comparative Examples 1 to 7.

[0202] Table 2 shows the results of tests conducted on the colored nylon slices produced in Examples 1 to 24 and the colored nylon provided in Comparative Examples 1 to 7, including tests for color intensity difference, sweat colorfastness, soap wash colorfastness, water colorfastness, and chromaticity of the supernatant liquid after steaming with an organic solvent. Visual observation of the color of the supernatant liquid obtained by steaming showed no change in chromaticity for the colored nylon slices produced in Examples 1 to 24. Measurements using the dilution factor method showed a chromaticity of less than 10 for the supernatant liquid, and demonstrated excellent water resistance and dye uniformity. Comparative Examples 1 to 4 and commercially available colored nylon showed a clear change in color of the supernatant liquid before and after steaming, indicating high chromaticity. The colored nylon produced in Comparative Examples 5 and 6 showed no significant change in the color of the supernatant after steaming with an organic solvent, but contained a large amount of residual halogen, had poor water resistance and dye uniformity, and furthermore, the reaction was time-consuming, the reaction efficiency was low, the reaction rate and utilization rate of the dye were low, the product purification process was complex, and a large amount of wastewater containing halogen and dye was generated.

[0203] [Table 2]

[0204] In Examples 1 to 24, the nylon monomer did not contain chlorine elements, and no halogen ions were generated throughout the reaction process. As a result, the boiled solutions corresponding to the nylon products produced by the manufacturing method according to the present invention did not contain free halogen ions, and did not fade even after steaming in an organic solvent. Furthermore, the dyeing was uniform, the stability was excellent, the colorfastness was high, and the performance in terms of sweat resistance, soap wash resistance, and water resistance was excellent.

[0205] Manufacturing Example 15 10.0 g of 1,4-diaminoanthraquinone and 78.5 g of adipic acid were sequentially added to a reactor, heated to 240°C under a nitrogen atmosphere, reacted at atmospheric pressure for 3 hours, vacuum was reduced to -0.05 MPa, and the reaction was continued at 240°C for 4 hours. Stirring was stopped to obtain the reaction solution, which was poured into a 250 mL beaker and cooled to room temperature. 100 mL of water was added to the beaker, and after boiling extraction, the extract was dried to obtain condensate 2-1. Its structural formula is shown in Table 3. 1 The 1H NMR spectrum is shown in Figure 5, and the infrared spectrum is shown in Figure 6. 1 The specific data for the 1H NMR spectrum is as follows:

[0206] 1 H NMR (400 MHz, DMSO): δ12.18 (s, 2H), 8.94-8.92 (m, 2H), 8.26 -8.22 (m, 1H), 7.92-7.87 (m, 2H), 7.53-7.52 (m, 1H), 2.74-2.72 (t, 4H), 2.29-2.27 (t, 4H), 1.65-1.57 (m, 8H).

[0207] Manufacturing Example 16 12.5 g of 1,2-diaminoanthraquinone and 1.52 g of dodecanedioic acid were sequentially added to a reactor, heated to 230°C under a nitrogen atmosphere, reacted for 4 hours at 0.08 MPa, then vacuum-suctioned to -0.06 MPa, continued the reaction at 230°C for 3 hours, stopped stirring to obtain the reaction solution, poured into a 250 mL beaker, cooled to room temperature, 125 mL of methanol was added to the beaker, and after heating and extraction, the extract was dried to obtain condensate 2-2. Its structural formula is shown in Table 3. 1 The 1H NMR data is as follows:

[0208] 11H NMR (400 MHz, DMSO): δ 8.35 - 8.29 (m, 6H), 8.04 - 7.95 (m, 2H), 7.58 - 7.51 (m, 2H), 7.19 - 7.06 (m, 2H), 2.53 - 2.35 (t, 4H), 1.53 - 1.40 (t, 4H), 1.41 - 1.35 (m, 6H), 1.33 - 1.25 (m, 6H).

[0209] Production Example 17 15.8 g of C.I. Disperse Blue - 56 and 0.58 g of adipic acid were sequentially added to the reactor. Under a nitrogen atmosphere, it was heated to 250 °C and reacted for 3 h under the condition of 0.12 MPa. Then, it was vacuum - suctioned to - 0.03 MPa, and the reaction was continued at 250 °C for 4 h. Stirring was stopped to obtain a reaction solution. The reaction solution was poured into a 250 - mL beaker, cooled to room temperature, 142 mL of methanol was added to the beaker, and after heating extraction, the extract was dried to obtain condensate 2 - 3. Its structural formula is shown in Table 3, 1 The 1H NMR spectrum is shown in Figure 7, and the infrared spectrum is shown in Figure 8. 1 The 1H NMR data are as follows.

[0210] 1 1H NMR (400 MHz, CDCl3): δ 7.58 - 7.54 (m, 2H), 7.32 - 7.30 (m, 2H), 7.05 - 7.02 (m, 2H), 5.35 (s, 4H), 2.46 - 2.44 (t, 2H), 2.27 - 2.24 (t, 2H), 1.76 - 1.73 (m, 4H).

[0211] Production Example 18 13.0 g of 1 - aminoanthraquinone and 92.3 g of glutaric acid were sequentially added to the reactor. Under a nitrogen atmosphere, it was heated to 235 °C and reacted for 5 h at normal pressure. Then, it was vacuum - suctioned to - 0.05 MPa, and the reaction was continued at 235 °C for 2 h. Stirring was stopped to obtain a reaction solution. The reaction solution was poured into a 250 - mL beaker, cooled to room temperature, 220 mL of ethanol was added to the beaker, and after heating extraction, condensate 2 - 4 was obtained. Its structural formula is shown in Table 4, 1 The 1H NMR data are as follows.

[0212] 1 H NMR (400 MHz, DMSO): δ 12.01 (s, 1H), 8.35 - 8.26 (m, 3H), 7.91 - 7.84 (m, 2H), 7.69 - 7.63 (m, 2H), 2.41 - 2.30 (t, 4H), 2.43 - 2.10 (m, 2H).

[0213] Production Example 19 10.4 g of adipic acid was added to a reactor, ethanol was added and dissolved, heated to 60 °C, 8.5 g of 1,4 - diaminoanthraquinone was weighed and dissolved in ethanol, then dropped into the reactor. After the dropping was completed, it was kept warm at normal pressure and reacted for 3 h. Ethanol was removed by rotary evaporation and dried to obtain a condensation salt. Deionized water was added to dissolve the above condensation salt, and a 40 wt% condensation salt - aqueous solution was prepared. Under a nitrogen environment, the temperature was raised to 230 °C and reacted at normal pressure for 5 h. Vacuum suction was carried out to -0.05 MPa, and the reaction was continued for 5 h. Then the reaction was terminated. The reaction solution was cooled to room temperature. After the reaction solution was filtered, the precipitate was washed with 30 mL of methanol and dried to obtain condensate 2 - 5. When detected by nuclear magnetic resonance method and infrared ray, its structural formula is shown in Table 3 and was the same as that of condensate 2 - 1.

[0214] Production Example 20 12.7 g of sebacic acid was added to a reactor, ethanol was added and dissolved, heated to 50 °C, 10 g of 1,4 - diaminoanthraquinone was weighed and dissolved in ethanol, then dropped into the reactor. After the dropping was completed, it was kept warm under the condition of 0.08 MPa and reacted for 3 h. Ethanol was removed by rotary evaporation and dried to obtain a condensation salt. Deionized water was added to dissolve the above condensation salt, and a 50 wt% condensation salt - aqueous solution was prepared. Under a nitrogen environment, the temperature was raised to 250 °C and reacted under the condition of 0.08 MPa for 5 h. Vacuum suction was carried out to -0.07 MPa, and the reaction was continued for 4 h. Then the reaction was terminated. The reaction solution was cooled to room temperature. After the reaction solution was filtered, the precipitate was washed with 68 mL of methanol and dried to obtain condensate 2 - 6. Its structural formula is shown in Table 3. 1 The H NMR data is as follows.

[0215] 1 H NMR (400MHz, DMSO): δ12.12 (s, 2H),8.95-8.91 (m, 4H), 8.24-8.19 (m, 2H), 8.04-7.92 (m, 4H), 7.55-7.53 (m, 2H), 2.36-2.24 (t,8H), 2.23-2.16 (t,4H), 1.57-1.41 (m,12H),1.35-1.22 (m,12H),1.19-1.10 (m,12H).

[0216] Manufacturing Example 21 15.7 g of adipic acid was added to the reactor, dissolved in ethanol, and heated to 70°C. 12.8 g of 2,6-diaminoanthraquinone was weighed and dissolved in ethanol, and added dropwise to the reactor. After the dropwise addition was complete, the reaction was maintained at 0.12 MPa for 4 hours. The ethanol was removed by rotary evaporation, and the mixture was dried to obtain the condensate salt. Deionized water was added to dissolve the condensate salt, and a 60 wt% aqueous solution of the condensate salt was prepared. Under a nitrogen environment, the temperature was raised to 200°C and the reaction was carried out at 0.12 MPa for 3 hours. The reaction was then continued for 6 hours under vacuum suction to -0.07 MPa, after which the reaction was terminated. The reaction solution was cooled to room temperature, filtered, and the precipitate was washed with 100 mL of deionized water and dried to obtain condensate 2-7. Its structural formula is shown in Table 3. 1 The 1H NMR spectrum is shown in Figure 9, and the infrared spectrum is shown in Figure 10. 1 The 1H NMR data is as follows:

[0217] 1 H NMR (400 MHz, DMSO):δ12.15 (s, 2H), 8.86-8.83 (m, 2H), 8.49-8.42 (m, 4H), 2.74-2.72 (t, 4H), 2.29-2.27 (t, 4H), 1.65-1.57 (m, 8H).

[0218] Manufacturing Example 22 9.9 g of isophthalic acid was added to the reactor, dissolved in ethanol, heated to 60°C, weighed 9.5 g of 1,2-diaminoanthraquinone and dissolved in ethanol, and added dropwise to the reactor. After the dropwise addition was complete, the reaction was carried out at 0.08 MPa for 5 hours, the ethanol was removed by rotary evaporation, and the mixture was dried to obtain the condensate salt. Deionized water was added to dissolve the condensate salt, and a 50 wt% aqueous solution of the condensate salt was prepared. Under a nitrogen environment, the temperature was raised to 230°C and the reaction was carried out at 0.12 MPa for 3 hours, then vacuum suction was applied to -0.06 MPa and the reaction was continued for 5 hours to terminate the reaction, the reaction solution was cooled to room temperature, the reaction solution was filtered, the precipitate was washed with 80 mL of deionized water, and the mixture was dried to obtain condensate 2-8. Its structural formula is shown in Table 3. 1 The 1H NMR data is as follows:

[0219] 1 H NMR (400MHz, DMSO): δ12.71 (s, 2H), δ8.45-8.40 (m, 3H), δ8.35-8.29 (m, 6H), δ8.26-8.23 (m, 3H), 8.16-8.14 (m, 3H), 8.04-7.95 (m, 2H), 7.69-7.67 (m, 3H), 7.58-7.51 (m,2H), 7.19 -7.06 (m, 2H).

[0220] Manufacturing Example 23 Condensate 2-1 was prepared according to the method of Production Example 15, except that the reaction process was modified as follows.

[0221] The mixture was heated to 270°C under a nitrogen atmosphere, reacted for 3 hours at 0.10 MPa, then vacuum-suctioned to -0.05 MPa, and the reaction was continued at 240°C for 4 hours. Stirring was then stopped to obtain the reaction solution.

[0222] Manufacturing Example 24 Condensate 2-1 was prepared according to the method of Production Example 15, except that the reaction process was modified as follows.

[0223] The mixture was heated to 240°C under a nitrogen atmosphere, reacted at atmospheric pressure for 3 hours, then vacuumed to -0.05 MPa, the reaction was continued at 250°C for 1 hour, and stirring was stopped to obtain the reaction solution.

[0224] Manufacturing Example 25 Condensates 2-5 were prepared according to the method of Production Example 19, except that the reaction process was modified as follows.

[0225] 10.4 g of adipic acid was added to the reactor, dissolved in ethanol, and heated to 40°C. 8.5 g of 1,4-diaminoanthraquinone was weighed and dissolved in ethanol, and added dropwise to the reactor. After the dropwise addition was complete, the mixture was kept warm at a pressure of 0.11 MPa for 3 hours. The ethanol was removed by rotary evaporation, and the mixture was dried to obtain a condensate salt. Deionized water was added to dissolve the condensate salt, and a 40 wt% aqueous solution of the condensate salt was prepared. The mixture was heated to 230°C under a nitrogen environment and reacted at atmospheric pressure for 5 hours. The mixture was then vacuum-suctioned to -0.05 MPa, and the reaction was continued for 5 hours before being terminated.

[0226] Manufacturing example 26 Condensates 2-5 were prepared according to the method of Production Example 19, except that the reaction process was modified as follows.

[0227] 10.4 g of adipic acid was added to the reactor, dissolved in ethanol, and heated to 60°C. 8.5 g of 1,4-diaminoanthraquinone was weighed and dissolved in ethanol, and added dropwise to the reactor. After the dropwise addition was complete, the reaction was carried out at atmospheric pressure for 6 hours. The ethanol was removed by rotary evaporation, and the mixture was dried to obtain a condensate salt. Deionized water was added to dissolve the condensate salt, and a 40 wt% aqueous solution of the condensate salt was prepared. The solution was heated to 240°C under a nitrogen environment, reacted at a pressure of 0.09 MPa for 5 hours, and then vacuum-suctioned to -0.05 MPa. The reaction was continued for 5 hours, after which the reaction was terminated.

[0228] [Table 3] JPEG2026508820000030.jpg38169

[0229] In Table 3, Xn is the number of structural units forming the condensate. For example, the number of structural units of A-(B-A)1 is 3, the number of structural units of A-(B-A)2 is 5, and the number of structural units of C-D is 2.

[0230] Example 25 1650 g of caprolactam, 9.9 g of benzoic acid, 1.28 g of condensate 2-7, and 82.5 mL of deionized water were added to a reaction kettle. After introducing nitrogen gas into the reaction kettle for 10 min, vacuum suction was performed for 10 min, and this was repeated 3 times to completely discharge the air in the kettle. The temperature was raised to 200 °C, and a ring-opening reaction was carried out for 0.5 h while stirring at normal pressure and a rotation speed of 400 r / min. The temperature was raised to 270 °C, and the pressure of the system was controlled to 1.2 MPa by removing excess water, and the reaction was carried out for 2.5 h. The temperature was lowered to 250 °C, the pressure of the system was released, and the reaction was continued at normal pressure for 1.5 h. Vacuum suction was performed until the pressure of the system reached -0.08 MPa. After reacting for 2 h, the reaction was stopped to obtain a reaction solution in a molten state. After cooling the reaction solution, it was sliced to obtain yellow nylon-6 polymer slices. Its infrared detection spectrum is shown in Figure 11, and a =C-H stretching vibration peak can be seen near 3085 cm -1 and a stretching vibration peak of the benzene skeleton can be seen near 1553 cm -1 .

[0231] Example 26 2000 g of nylon-66 salt, 11.8 g of adipic acid, 1.78 g of condensate 2-7, and 152 ml of deionized water were added to a reaction kettle. After introducing nitrogen gas into the reaction kettle for 10 min, vacuum suction was performed for 10 min, and this was repeated 3 times to completely discharge the air in the kettle. Under a nitrogen atmosphere, it was heated to 200 °C, stirred at a rotation speed of 450 r / min, and the pressure of the system was maintained at 1.8 MPa by removing the water in the system, and the reaction was carried out at a constant temperature for 3.5 h. Then, the pressure of the system was released to normal pressure, the temperature was raised to 270 °C, vacuum suction was performed until the pressure of the system reached -0.09 MPa, and after continuing the reaction for 2.5 h, the reaction was stopped to obtain a reaction solution in a molten state. The stirrer was stopped, the melt reaction solution in the reaction kettle was poured out, cooled to room temperature, sliced, and yellow nylon-66 polymer slices were obtained.

[0232] Example 27 1250 g of nylon-1010 salt, 2.92 g of adipic acid, 1.39 g of condensate 2-7, and 115 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 min, followed by vacuum suction for 10 min. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 215°C and stirred at 400 r / min. The system pressure was maintained at 1.7 MPa by removing water from the system, and the reaction was carried out at a constant temperature for 2 hours. After that, the system pressure was released to atmospheric pressure, the temperature was raised to 270°C, and the system pressure was vacuum suctioned until it reached -0.07 MPa. The reaction was continued for 3 hours, after which the reaction was stopped to obtain a molten reaction solution. The stirrer was stopped, the melted reaction solution was poured out of the reaction vessel, cooled to room temperature, and sliced ​​to obtain yellow nylon-1010 polymer slices.

[0233] Example 28 1500g of nylon-612 salt, 4.59g of adipic acid, 18.75g of condensate 2-7, and 85ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by vacuum suction for 10 minutes. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 220°C and stirred at 450 r / min to remove water from the system, maintaining the system pressure at 1.8 MPa. The reaction was then carried out at a constant temperature for 2.5 hours. After that, the system pressure was released to atmospheric pressure, the temperature was raised to 225°C, and the system pressure was vacuum suctioned until it reached -0.09 MPa. The reaction was continued for 2.5 hours, after which the reaction was stopped to obtain a molten reaction solution. The stirrer was stopped, the melted reaction solution was poured out of the reaction vessel, cooled to room temperature, and sliced ​​to obtain yellow nylon-612 polymer slices.

[0234] Example 29 1125 g of caprolactam, 10.1 g of benzoic acid, 22.5 g of condensate 2-6, and 63.2 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 min, followed by vacuum suction for 10 min. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 230°C, and the ring-opening reaction was carried out for 0.5 hours with stirring at a pressure of 0.12 MPa and a rotation speed of 400 r / min. The temperature was raised to 260°C, and the pressure of the system was controlled to 1.5 MPa by removing excess water, and the reaction was carried out for 2.5 hours. The temperature was lowered to 240°C, the pressure of the system was released, and the reaction was continued for 1.5 hours at a pressure of 0.12 MPa. Vacuum suction was applied until the pressure of the system became -0.09 MPa, and after 2 hours of reaction, the reaction was stopped to obtain a molten reaction solution. After the reaction solution was cooled, it was sliced ​​to obtain brown nylon-6 polymer slices.

[0235] Example 30 1300 g of nylon-66 salt, 4.20 g of adipic acid, 0.9 g of condensate 2-6, and 138 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 min, followed by vacuum suction for 10 min. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 230°C and stirred at 500 r / min to remove water from the system, maintaining a system pressure of 1.5 MPa. The reaction was then carried out at a constant temperature for 4 hours. After that, the system pressure was released to atmospheric pressure, the temperature was raised to 250°C, and the system pressure was vacuum suctioned until it reached -0.06 MPa. The reaction was continued for 1 hour, then stopped to obtain the reaction solution. The stirrer was stopped, the melt reaction solution was poured out of the reaction vessel, cooled to room temperature, and sliced ​​to obtain brown nylon-66 polymer slices.

[0236] Example 31 1000 g of caprolactam, 7.30 g of benzoic acid, 2.25 g of condensate 2-3, and 50 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 min, followed by vacuum suction for 10 min. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 220°C, and the ring-opening reaction was carried out for 1 hour with stirring at a pressure of 0.08 MPa and a rotation speed of 450 r / min. The temperature was raised to 245°C, and the pressure of the system was controlled to 1.3 MPa by removing excess water, and the reaction was continued for 3.5 hours. The temperature was lowered to 235°C, the pressure of the system was released, and the reaction was continued for 1.0 hour at a pressure of 0.08 MPa. Vacuum suction was applied until the pressure of the system became -0.08 MPa, and after 1.5 hours of reaction, the reaction was stopped to obtain a molten reaction solution. After the reaction solution was cooled, it was sliced ​​to obtain black nylon-6 polymer slices. The infrared detection spectrum is shown in Figure 12, at 3085 cm⁻¹. -1 A peak in the CH stretching vibration is observed nearby, at 1553 cm. -1 A stretching vibration peak of the benzene skeleton can be seen in the vicinity.

[0237] Example 32 1560 g of nylon-1010 salt, 4.09 g of adipic acid, 1.77 g of condensate 2-3, and 104.0 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 min, followed by vacuum suction for 10 min. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 230°C and stirred at 400 r / min to remove water from the system, maintaining a system pressure of 1.38 MPa. The reaction was then carried out at a constant temperature for 4 hours. After that, the system pressure was released to atmospheric pressure, the temperature was raised to 270°C, and the system pressure was vacuum suctioned until it reached -0.09 MPa. The reaction was continued for 2.5 hours, after which the reaction was stopped to obtain the reaction solution. The stirrer was stopped, the melt reaction solution in the reaction vessel was poured out, cooled to room temperature, and sliced ​​to obtain black nylon-1010 polymer slices.

[0238] Example 33 1500 g of caprolactam, 8.10 g of benzoic acid, 10.82 g of condensate 2-4, and 68.2 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 min, followed by vacuum suction for 10 min. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 230°C, and the ring-opening reaction was carried out for 0.5 hours with stirring at atmospheric pressure and a rotation speed of 400 r / min. The temperature was raised to 250°C, and the system pressure was controlled to 1.5 MPa by removing excess water, and the reaction was continued for 2.5 hours. The temperature was lowered to 240°C, the system pressure was released, and the reaction was continued at atmospheric pressure for 1.0 hour. Vacuum suction was applied until the system pressure was -0.09 MPa, and after 1.5 hours of reaction, the reaction was stopped. A molten reaction solution was obtained, the reaction solution was cooled, and then sliced ​​to obtain orange nylon-6 polymer slices.

[0239] Example 34 1530.0 g of nylon-612 salt, 6.58 g of adipic acid, 12.8 g of condensate 2-4, and 102.0 ml of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 min, followed by vacuum suction for 10 min. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 220°C and stirred at a rotation speed of 450 r / min to remove water from the system, maintaining the system pressure at 1.80 MPa. The reaction was then carried out at a constant temperature for 2 hours. After that, the system pressure was released to atmospheric pressure, the temperature was raised to 270°C, and the system pressure was vacuum suctioned until it reached -0.06 MPa. The reaction was continued for 3 hours, then stopped to obtain the reaction solution. The stirrer was stopped, the melted reaction solution was poured out of the reaction vessel, cooled to room temperature, and sliced ​​to obtain orange nylon-612 polymer slices.

[0240] Example 35 Yellow nylon-6 polymer slices were prepared according to the method of Example 25, except that the amount of benzoic acid used was changed to 5.2 g.

[0241] Example 36 Yellow nylon-6 polymer slices were prepared according to the method of Example 25, except that the amount of benzoic acid used was changed to 4.5 g.

[0242] Example 37 Yellow nylon-66 polymer slices were prepared according to the method of Example 26, except that the amount of nylon-66 salt used was changed to 3000g.

[0243] Example 38 Yellow nylon-6 polymer slices were produced according to the method of Example 25, except that the reaction process was modified as follows. Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by 10 minutes of vacuum suction. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 280°C, and the ring-opening reaction was carried out for 1.5 hours with stirring at a pressure of 0.11 MPa and a rotation speed of 400 r / min. The temperature was raised to 270°C, and the pressure of the system was controlled to 1.2 MPa by removing excess water, and the reaction was continued for 2.5 hours. The temperature was lowered to 250°C, the pressure of the system was released, and the reaction was continued at atmospheric pressure for 1.5 hours. Vacuum suction was applied until the pressure of the system reached -0.08 MPa, and after 2 hours of reaction, the reaction was stopped to obtain the reaction solution.

[0244] Example 39 Yellow nylon-6 polymer slices were produced according to the method of Example 25, except that the reaction process was modified as follows.

[0245] Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by vacuum suction for 10 minutes. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 200°C, and the ring-opening reaction was carried out for 0.5 hours at atmospheric pressure and with stirring at 400 r / min. The temperature was raised to 250°C, and the system pressure was controlled to 1.4 MPa by removing excess water, and the reaction was continued for 2.5 hours. The temperature was lowered to 240°C, the system pressure was released, and the reaction was continued at atmospheric pressure for 0.5 hours. Vacuum suction was applied until the system pressure reached -0.08 MPa, and after 0.5 hours of reaction, the reaction was stopped to obtain the reaction solution.

[0246] Example 40 Yellow nylon-6 polymer slices were produced according to the method of Example 25, except that the reaction process was modified as follows.

[0247] Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by 10 minutes of vacuum suction. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 200°C, and the ring-opening reaction was carried out for 0.5 hours at atmospheric pressure and with stirring at 400 r / min. The temperature was raised to 270°C, and the system pressure was controlled to 1.2 MPa by removing excess water, and the reaction was continued for 2.5 hours. The temperature was lowered to 260°C, the system pressure was released, and the reaction was continued at atmospheric pressure for 1.5 hours. Vacuum suction was applied until the system pressure reached -0.08 MPa, and after 2 hours of reaction, the reaction was stopped to obtain the reaction solution.

[0248] Example 41 Yellow nylon-6 polymer slices were produced according to the method of Example 25, except that the reaction process was modified as follows.

[0249] Nitrogen gas was introduced into the reaction vessel for 10 minutes, followed by 10 minutes of vacuum suction. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 200°C, and the ring-opening reaction was carried out for 0.5 hours at atmospheric pressure and with stirring at 400 r / min. The temperature was raised to 270°C, and the system pressure was controlled to 1.2 MPa by removing excess water, and the reaction was continued for 2.5 hours. The temperature was lowered to 220°C, the system pressure was released, and the reaction was continued at atmospheric pressure for 1.5 hours. Vacuum suction was applied until the system pressure reached -0.06 MPa, and after 2 hours of reaction, the reaction was stopped to obtain the reaction solution.

[0250] Example 42 Yellow nylon-66 polymer slices were produced according to the method of Example 26, except that the reaction process was modified as follows.

[0251] After introducing nitrogen gas into the reaction vessel for 10 minutes, vacuum suction was performed for 10 minutes, and this process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 220°C and stirred at a rotation speed of 450 r / min to remove water from the system, maintaining the system pressure at 2.1 MPa, and the reaction was carried out at a constant temperature for 3.5 hours. Subsequently, the system pressure was released to atmospheric pressure, the temperature was raised to 270°C, and vacuum suction was performed until the system pressure reached -0.09 MPa, and the reaction was continued for 2.5 hours, after which the reaction was stopped to obtain the reaction solution.

[0252] Example 43 Yellow nylon-66 polymer slices were produced according to the method of Example 26, except that the reaction process was modified as follows.

[0253] After introducing nitrogen gas into the reaction vessel for 10 minutes, vacuum suction was performed for 10 minutes, and this process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 200°C and stirred at a rotation speed of 450 r / min to remove water from the system, maintaining the system pressure at 1.8 MPa, and the reaction was carried out at a constant temperature for 3.5 hours. Subsequently, the system pressure was released to atmospheric pressure, the temperature was raised to 220°C, and vacuum suction was performed until the system pressure became -0.06 MPa, and the reaction was continued for 2.5 hours, after which the reaction was stopped to obtain the reaction solution.

[0254] Example 44 Brown nylon-6 polymer slices were prepared according to the method of Example 25, except that condensate 2-7 was replaced with condensate 2-1. Its infrared detection spectrum is shown in Figure 13, at 3085 cm⁻¹. -1 A peak in the CH stretching vibration is observed nearby, at 1553 cm. -1 A stretching vibration peak of the benzene skeleton can be seen in the vicinity.

[0255] Example 45 Brown nylon-6 polymer slices were prepared according to the method of Example 25, except that condensate 2-7 was replaced with condensate 2-2.

[0256] Example 46 Brown nylon-66 polymer slices were prepared according to the method of Example 26, except that condensate 2-7 was replaced with condensate 2-5.

[0257] Example 47 Brown nylon-66 polymer slices were prepared according to the method of Example 26, except that condensate 2-7 was replaced with condensate 2-8.

[0258] Example 48 1530 g of poly(p-phenylene terephthalamide) (PPTA monomer), 6.58 g of adipic acid, 12.8 g of condensate 2-7, and 102 mL of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 mins, followed by vacuum suction for 10 mins. This process was repeated three times to completely remove the air from the vessel. Under a nitrogen atmosphere, the mixture was heated to 220°C, and stirring was started at a stirring speed of 450 rpm. The system pressure was maintained at 1.80 MPa by removing water from the system, and the reaction was carried out at a constant temperature for 2 hours. After that, the system pressure was released to atmospheric pressure (pressure release time was approximately 1.5 hours). Finally, the temperature was further increased to 270°C, and the system pressure was vacuum suctioned until it reached -0.06 MPa. The reaction was continued for 3 hours, the reaction was stopped, the stirrer was stopped, the melt in the reaction vessel was poured out, cooled to room temperature, and sliced ​​to obtain a yellow aromatic nylon product.

[0259] Comparative Example 8 Nylon-6 was dyed by immersion dyeing using bat yellow GCN, which is produced from 2,6-diaminoanthraquinone, as the dye. The specific procedure was as follows: An aqueous solution containing 2.5 g / L bat yellow GCN, 3 g / L sodium dithionite, and 2 g / L sodium hydroxide was prepared and kept warm at 20°C for 40 mins to obtain a sufficiently reduced vat dye leuco. Nylon-6 was added to the vat dye leuco solution and kept warm at 50°C for 40 mins with a bath ratio of 1:10. After dyeing was complete, the nylon-6 was washed with water, then oxidized with 1 g / L hydrogen peroxide, followed by soap washing, water washing, and baking to obtain yellow nylon.

[0260] Comparative Example 9 Yellow nylon was manufactured according to the method of Comparative Example 8, except that nylon 6 was replaced with nylon-66.

[0261] Comparative Example 10 Yellow nylon was manufactured according to the method of Comparative Example 8, except that nylon 6 was replaced with nylon-1010.

[0262] Comparative Example 11 Yellow nylon was manufactured according to the method of Comparative Example 8, except that nylon 6 was replaced with nylon-612.

[0263] Comparative Example 12 Black nylon was produced according to the method of Comparative Example 8, except that the bat yellow GCN produced with 2,6-diaminoanthraquinone was replaced with disperse blue-56.

[0264] Comparative Example 13 Black nylon was manufactured according to the method of Comparative Example 12, except that nylon 6 was replaced with nylon-1010.

[0265] Comparative Example 14 1650 g of caprolactam, 9.9 g of benzoic acid, 1.28 g of 2,6-diaminoanthraquinone, and 82.5 mL of deionized water were added to the reaction vessel. Nitrogen gas was introduced into the reaction vessel for 10 min, followed by vacuum suction for 10 min. This process was repeated three times to completely remove the air from the vessel. The temperature was raised to 200°C, and the ring-opening reaction was carried out for 0.5 hours at atmospheric pressure and with stirring at 400 r / min. The temperature was raised to 270°C, and the pressure of the system was controlled to 1.2 MPa by removing excess water, and the reaction was continued for 2.5 hours. The temperature was lowered to 250°C, the pressure of the system was released, and the reaction was continued at atmospheric pressure for 1.5 hours. Vacuum suction was applied until the pressure of the system was -0.08 MPa, and after 2 hours of reaction, the reaction was stopped to obtain a molten reaction solution. After the reaction solution was cooled, it was drawn into wire and pelletized, extracted with water, dried, and sliced ​​to obtain yellow nylon-6 polymer slices.

[0266] Comparative Example 15 2000 g of nylon-66 salt, 11.8 g of adipic acid, 1.78 g of 2,6-diaminoanthraquinone, and 152 ml of deionized water were added to a reaction kettle. After introducing nitrogen gas into the reaction kettle for 10 min, vacuum suction was performed for 10 min, and this was repeated 3 times to completely exhaust the air in the kettle. Under a nitrogen atmosphere, it was heated to 200 °C, stirred at a rotation speed of 450 r / min, and the pressure of the system was maintained at 1.8 MPa by removing the water in the system, and the reaction was carried out at a constant temperature for 3.5 h. Then, the pressure of the system was released to normal pressure, the temperature was raised to 270 °C, vacuum suction was performed until the pressure of the system reached -0.09 MPa, the reaction was continued for 2.5 h, and then the reaction was stopped to obtain a molten reaction solution. The stirrer was stopped, the melt reaction solution in the reaction kettle was poured out, cooled to room temperature, extracted with water, dried and sliced to obtain yellow nylon-66 polymer slices.

[0267] Test Example 2 For the colored nylon slices produced in Examples 25 to 48 and the colored nylon provided in Comparative Examples 8 to 15, the content of the chromogenic structural unit was determined by nuclear magnetic resonance method and infrared spectroscopy respectively, and the results are shown in Table 4.

[0268] For the colored nylon produced in Examples 25 to 48, infrared detection was performed respectively. In each infrared spectrum, a =C-H stretching vibration peak was observed near 3085 cm -1 and a stretching vibration peak of the benzene nucleus skeleton was observed near 1553 cm -1 . For the colored nylon provided in Comparative Examples 8 to 13, infrared detection was performed respectively, and characteristic peaks were also observed near 3085 cm -1 and 1553 cm -1 , but the peak values were relatively small and the characteristic peaks were not clear.

[0269] For the colored nylon produced in Examples 25 to 48 and the colored nylon provided in Comparative Examples 8 to 13, the test results of the difference in color density, the test of color fastness to perspiration, the test of color fastness to soap washing, the test of color fastness to water, and the test of the chromaticity of the supernatant by organic solvent steaming are shown in Table 4.

[0270] In a test of the difference in color intensity, it was found that the difference in color intensity of the 6 slices of yellow nylon produced in Example 25 was significantly smaller than that of the 6 slices of yellow nylon produced in Comparative Example 14, and the difference in color intensity of the 6 slices of yellow nylon produced in Example 26 was significantly smaller than that of the 6 slices of yellow nylon produced in Comparative Example 15. This indicates that, in the same nylon manufacturing system, in Comparative Examples 14 and 15, the dye is directly copolymerized with the nylon monomer, resulting in low reaction efficiency, incomplete dyeing reaction, poor uniformity of the nylon dyeing effect, and the need to wash with water after the reaction to remove unreacted dye, which generates a large amount of dye-containing wastewater. On the other hand, in Examples 25 and 26, by copolymerizing the dye with the nylon monomer in the form of a condensate, a high reactivity ratio between the dye color-developing group and the nylon monomer can be achieved, and the dye color-developing group can be efficiently introduced into the nylon segment, resulting in high dyeing efficiency, full utilization of the dye, excellent dyeing uniformity, high stability, and maintenance of the excellent mechanical properties and water resistance of the nylon product. Figure 3 shows a comparison of the black nylon 6 polymer slices produced in Example 31 before and after steaming with ethyl acetate (there are some color differences in the images due to differences in lighting and angle). The chromaticity of the solution after steaming is extremely low. Figure 4 shows a comparison of the black nylon 6 produced in Comparative Example 12 before and after steaming with ethyl acetate. The color of the supernatant before and after steaming changes from colorless to purple, and the chromaticity value of the supernatant increases significantly after steaming.

[0271] [Table 4]

[0272] The results in Table 4 show that the colored nylon obtained by the manufacturing method according to the present invention exhibits uniform dyeing, controllable color, excellent stability, high colorfastness, and excellent properties such as sweat resistance, soap washing resistance, and water resistance, and does not fade even after steaming in an organic solvent. The manufacturing method for colored nylon according to the present invention can avoid the generation of by-products containing halogen ions and can reduce energy consumption, water consumption, chemical consumption, and wastewater discharge in the dyeing process.

[0273] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, several simple modifications can be made to the technical solutions of the present invention, including combining each technical feature in any other suitable manner, and these simple modifications and combinations should also be considered as part of the disclosure of the present invention and all fall within the scope of protection of the present invention. [Brief explanation of the drawing]

[0274] [Figure 1] These are the infrared spectra of the dye monomer, dibasic acid, and dye condensate 1-1 in Production Example 1. [Figure 2] This shows the infrared spectra of dye condensate 1-1, caprolactam, and colored nylon in Example 1. [Figure 3] This is a comparison diagram of the black nylon-6 polymer slices produced in Example 31 before and after steaming with ethyl acetate, where a is before steaming and b is after steaming. [Figure 4] This is a comparison diagram of black nylon-6 produced in Comparative Example 12 before and after steaming with ethyl acetate, where a is before steaming and b is after steaming. [Figure 5] This is the 1H NMR spectrum of condensate 2-1, which was prepared in manufacturing example 15. [Figure 6] This is the infrared spectrum of condensate 2-1 produced in manufacturing example 15. [Figure 7] This is the 1H NMR spectrum of condensate 2-3 prepared in manufacturing example 17. [Figure 8]This is the infrared spectrum of condensate 2-3 produced in manufacturing example 17. [Figure 9] This is the 1H NMR spectrum of condensate 2-7 prepared in manufacturing example 21. [Figure 10] This is the infrared spectrum of condensate 2-7 produced in manufacturing example 21. [Figure 11] This is the infrared spectrum of the yellow nylon-6 polymer produced in Example 25. [Figure 12] This is the infrared spectrum of the black nylon-6 polymer produced in Example 31. [Figure 13] This is the infrared spectrum of the brown nylon-6 polymer produced in Example 44. [Figure 14] These are the 1H NMR spectra of the condensate, dye monomer, and dibasic acid produced in Production Example 2. [Figure 15] This is a liquid chromatogram of the condensate, dye monomer, and dibasic acid produced in Production Example 2.

Claims

1. It is made of colored nylon, The colored nylon is characterized in that it contains nylon structural units and color-developing structural units, the color-developing structural units contain dye color-developing groups, the chromaticity of the supernatant liquid obtained by mixing the colored nylon and an organic solvent in a weight ratio of 1:3 and steaming is 10 or less, and the difference in color intensity of the colored nylon is 0.2 or less.

2. The colored nylon according to claim 1, characterized in that the halogen ion content in the boiled solution obtained by mixing the colored nylon and deionized water in a weight ratio of 1:1 and steaming is 5 ppm or less.

3. The colored nylon according to claim 1 or 2, characterized in that the colored nylon has a water colorfastness rating of 4 to 5, a sweat colorfastness rating of 4 to 5, and a soap wash colorfastness rating of 4 to 5.

4. The aforementioned dye coloring group is at least one selected from anthraquinone coloring group, solvent black group, acid black group, acid blue group, and acid yellow group. Preferably, the colored nylon according to any one of claims 1 to 3, wherein the content of the color-developing structural units is 0.2 to 1.5% by weight, based on the weight of the colored nylon.

5. A method for manufacturing colored nylon, A method for producing colored nylon, characterized by comprising the step of bringing a condensate containing dye coloring groups into contact with a nylon monomer to carry out a condensation reaction so that at least a portion of the dye coloring groups are located between and / or at the ends of structural units formed by nylon units.

6. The manufacturing method according to claim 5, characterized in that the structural formula of the condensate containing the dye color group is represented by formula (I). 【Chemistry 1】 (Here, R １ (where Q' is an aliphatic alkylene or aromatic alkylene, and Q' is the dye coloring group.)

7. The manufacturing method according to claim 6, characterized in that the structural formula of the dye coloring group is at least one selected from formula (II), formula (III), and formula (IV). 【Chemistry 2】 (Here, R Ｉ , R ＩＩ , R ＩＩＩ , R ＩＶ , and R Ｖ (Each of these is independently a hydrogen atom and / or a water-soluble group, and p is an integer between 1 and 10.)

8. The water-soluble group is -(CR ＶＩ R ＶＩＩ ), ｍ’ -SO ３ M, where R ＶＩ , R ＶＩＩ are each independently at least one selected from hydrogen and C1-C5 alkyl, M is a monovalent metal ion and / or an ammonium ion, and m' is an integer from 0 to 4. The production method according to claim 7, characterized in that.

9. The manufacturing method according to claim 6, characterized in that the dye coloring group is an anthraquinone group represented by formula (V) which is either unsubstituted or substituted. 【Transformation 3】

10. The manufacturing method according to claim 5, characterized in that the condensate containing the dye coloring group contains two terminal aminos or two terminal carboxyls and has a structural unit a represented by formula (VI). 【Chemistry 4】 (Here, R ２ (wherein Q'' is an aliphatic alkylene or aromatic alkylene, and Q'' is the dye coloring group.)

11. The manufacturing method according to claim 10, characterized in that the dye color-developing group is an unsubstituted or substituted group represented by formula (VII), or an unsubstituted or substituted group represented by formula (VIII). 【Transformation 5】

12. The manufacturing method according to any one of claims 5 to 11, characterized in that the manufacturing process for the condensate containing the dye chromogenic group comprises the step of carrying out a reaction I with a dye monomer containing the dye chromogenic group and a dibasic acid, and removing the unreacted dye monomer containing the dye chromogenic group and / or the dibasic acid.

13. The production method according to claim 12, characterized in that the dibasic acid is an aliphatic C2-C16 dibasic acid and / or an aromatic C8-C14 dibasic acid, preferably at least one selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, terephthalic acid, phthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.

14. The manufacturing method according to claim 12, characterized in that the molar ratio of the dye monomer to the dibasic acid is 1:0.01 to 100, more preferably 1:2 to 50.

15. The process of reaction I includes the steps of sequentially performing the first-stage reaction I and the second-stage reaction I by mixing the dye monomer and the dibasic acid under oxygen-free conditions. Preferably, the conditions for the first-stage reaction I include at least a temperature of 200 to 250°C, a pressure of 0.08 to 0.12 MPa, and a time of 3 to 5 hours. The manufacturing method according to claim 12, characterized in that the conditions for the second-stage reaction I include at least a temperature of 200 to 250°C, a pressure of -0.03 to -0.06 MPa, and a time of 2 to 10 hours.

16. The process of reaction I includes the steps of mixing the dye monomer and the dibasic acid to carry out reaction I to obtain a condensed salt, and then sequentially carrying out first-stage reaction II and second-stage reaction II on the condensed salt under oxygen-free conditions. Preferably, the conditions for the mixed reaction I include at least a temperature of 50 to 70°C, a pressure of 0.08 to 0.12 MPa, and a time of 1 to 5 hours. The conditions for the first-stage reaction II include at least a temperature of 200 to 250°C, a pressure of 0.08 to 0.12 MPa, and a time of 1 to 5 hours. The manufacturing method according to claim 12, characterized in that the conditions for the second-stage reaction II include at least a temperature of 200 to 250°C, a pressure of -0.04 to -0.09 MPa, and a time of 2 to 8 hours.

17. The manufacturing method according to any one of claims 5 to 11, characterized in that the weight ratio of the condensate containing the dye coloring group to the nylon monomer is 1:50 to 3000, more preferably 1:50 to 1500.

18. The nylon monomer is a lactam, preferably a C2-C20 lactam, more preferably at least one of caprolactam, undecane lactam, and lauryl lactam. The manufacturing method according to any one of claims 5 to 11, characterized in that the condensation reaction is carried out in the presence of an auxiliary agent, the auxiliary agent being an organic monobasic acid, preferably an aliphatic monobasic acid and / or an aromatic monobasic acid, more preferably an aromatic monobasic acid, and even more preferably benzoic acid.

19. The nylon monomer is at least one selected from aliphatic nylon salts, preferably nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt, nylon 1313 salt, nylon 1012 salt, and nylon 1010 salt. The manufacturing method according to any one of claims 5 to 11, characterized in that the condensation reaction is carried out in the presence of an auxiliary agent, the auxiliary agent being an organic dibasic acid, preferably an aliphatic dibasic acid and / or an aromatic dibasic acid, more preferably an aliphatic dibasic acid, and even more preferably a C4-C8 dibasic acid.

20. The manufacturing method according to any one of claims 5 to 11, further comprising the step of cooling and processing the product of the condensation reaction.

21. Colored nylon manufactured by the manufacturing method described in any one of claims 5 to 20.

22. Use of colored nylon according to any one of claims 1 to 4 and 21 in at least one of spinning, industrial fibers, and engineering materials.

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